Thermoplastic elastomeric resin composition and a process for the preparation thereof

ABSTRACT

The invention provides a process for the preparation of a thermoplastic elastomeric resin composition comprising melt kneading 
     (a) 100 parts by weight of a block copolymer consisting of at least two polymeric blocks (A) composed mainly of a vinyl aromatic compound and at least one polymeric block (B) composed mainly of a conjugated diene compound, and/or a hydrogenated block copolymer obtained by hydrogenating said block copolymer, 
     (b) 20 to 300 parts by weight of a non-aromatic softening agent for rubber, 
     (c) 1 to 150 parts by weight of a peroxide-crosslinking type olefinic resin and/or a copolymeric rubber containing said resin, and 
     (d) 10 to 150 parts by weight of a peroxide-decomposing type olefinic resin and/or a copolymer containing said resin, 
     characterized in that the process comprises a step of heat-processing component (a), component (b), at least a part of component (c), at least a part of component (d) and at least a part of 1.0 to 1,200 parts by weight of component (e) in the presence of an organic peroxide to cause crosslinking, wherein component (e) is at least one thermoplastic polymer selected from the group consisting of polyester type (co)polymers, polyamide type (co)polymers and polyurethane type (co)polymers, and a subsequent step of blending these with the remaining part of component (c), and, the remaining part of component (d) and component (e), if any. The obtained composition is soft and excellent in heat deformation resistance and mechanical strength, moldability and processability, particularly in oil resistance and stain resistance.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of, commonly assigned, U.S. patentapplication Ser. No. 08/864,061, filed May 27, 1997, now U.S. Pat. No.5,936,037.

FIELD OF THE INVENTION

The present invention relates to a thermoplastic elastomeric resincomposition and a process for the preparation thereof.

The present composition may be added as a softening agent to athermoplastic elastomer such as polyester type resins, polyolefine typeresins, plyurethane type resins, vinyl aromatic type resins andpolyamide type resins.

PRIOR ART

Thermoplastic elastomeric resins which are rubber-like materials, do notneed a vulcanization process and have thermoplastic resin-like moldingprocessability are attracting attention in the fields of auto parts,parts for electric appliances, electric wire insulation, footwears andgeneral goods.

Various types of such thermoplastic elastomeric resins have beendeveloped and put on sale, such as polyolefine type, polyurethane type,polyester type, polystyrene type, polyvinyl chloride type and polyamidetype.

Among those, polystyrene type thermoplastic elastomeric resins such asstyrene-butadiene block copolymers (SBS) and styrene-isoprene blockcopolymers (SIS) and hydrogenated resins thereof have high softness andgood rubber elasticity at normal temperature. Further, thermoplasticelastomeric resin compositions obtained from these show goodprocessability.

However, these polymers have problems in resistance to weathering asthey have double bonds in conjugated diene blocks in molecule.

To overcome the problems, the double bonds in block copolymers ofstyrene and conjugated diene are hydrogenated to give elastomeric resinswith improved thermal stability.

Several thermoplastic elastomeric resin compositions of suchhydrogenated ones have been proposed, for instance, in Japanese PatentApplication Laid-Open (hereinafter refereed to as JP Laid-Open) Nos.50-14742/1975 and 52-26551/1977. As modification of these, JP Laid-OpenNos. 58-13203211983, 58-145751/1983, 59-53548/1984 and 62-48757 disclosecompositions comprising a hydrogenated styrene-conjugated diene blockcopolymer, a hydrocarbon and an alpha-olefin polymeric resin, and aprocess for the preparation thereof.

Unfortunately, the thermoplastic elastomeric resin compositions of theprior art comprising such hydrogenated block copolymers have a drawbackin rubber properties, such as deformation under heat and pressure(compression set) and rubber elasticity at a high temperature.

To solve such a drawback, there have been proposed a cross-linkingcomposition in which a silane compound is added to a compositioncontaining such a hydrogenated block copolymer, and cross-linked oneobtained by cross-linking a composition containing such a hydrogenatedblock copolymer in the presence of an organic peroxide, for instance, inJP Laid-Open Nos. 59-6236/1984 and 63-57662/1987, Japanese PatentPublication Nos. 3-49927/1991,3-11291/1991 and 6-13628/1994.

However, such proposed cross-linked compositions of the hydrogenatedblock copolymer are unsatisfactory in compression set at a hightemperature, particularly at 100° C. and, moreover, tensile propertiesdeteriorate considerably at 80° C. or more. Further, such compositionsdo not meet the levels of properties required in the fields ofvulcanized rubber. Particularly, good processability cannot be attained,and the mechanical strength is low.

To solve such drawbacks, in JP Laid-Open No. 4-20549/1992, there isdesclosed a polymer in which a component composed of carboxylic acidderivatives and/or epoxy derivatives is copolymerized with or graftpolymerized to such a block copolymer, or in which other polymers aregraft or block bonded to such a block copolymer, and, further, apolyamide type polymer and/or polyester type polymer are added to acomposition of a hydrogenated block copolymer, and crosslinked in thepresence of an organic peroxide.

However, the crosslinked composition of the hydrogenated block copolymerdesclosed has problems. That is, compression set at a high temperature,particularly at 100° C. or more is high and tensile properties are poor.Further, balance between compression set and hardness is bad.

In addition, in the case of blending polyamide type polymer, polyestertype polymer and/or polyurethane type polymer, hardness is not less thanHSA 85, which is little different from that of polyamide type polymer,polyester type polymer or polyurethane type polymer.

In JP Laid-Open Nos. 1-139241/1989 and 3-100045/1991, there is descloseda melting blended substance of a thermoplastic elastic body selectedfrom hydrogenated SBS block copolymers, olefin type elastomers, dienetype elastomers, urethane type elastomers and plasticized polyvinylchlorides and a polyester type thermoplastic elastomer or a polyetherblock amide.

However, this composition is poor in balance between compression set andhardness and shows unsufficient compatibility, so that the abrasionresistance is bad.

Further, JP Laid-Open No. 5-214209/1993 discloses a composition in whicha modified polystyrene type resin and/or a modified polyolefin typeresin having an epoxy, acid anhydride or oxazoline group is added to acomposition containing a hydrogenated derivative of a block copolymerand a polyester typer resin, whereby the composition is improved incompatibility and excellent in softness, heat resistance and chemicalresistance. JP Publication No. 5-75016/1993 (i.e., Laid Open No.1-230660/1998) discloses a composition which comprises a hydrogenatedderivative of a block copolymer and a hydrogenated derivative having acarboxylic acid group or a derivative group thereof together with apolyolefin resin and a thermoplastic polyester. JP Laid-Open Nos.3-234745/1991, 3-234755/1991, 5-171003/1993 and 7-126474/1995 disclose acomposition which comprises a hydrogenated derivative of a blockcopolymer and a hydrogenated derivative having a carboxylic acid groupor a derivative group thereof together with a thermoplasticpolyurethane. JP Laid-Open No. 2-97554/1990 discloses a compositionwhich comprises a hydrogenated derivative of a block copolymer and ahydrogenated derivative having an epoxy group or a derivative groupthereof together with a thermoplastic polyurethane.

However, those components have drawbacks. That is, compression set at ahigh temperature, particularly at 100° C. or more is high and tensileproperties are poor. In addition, balance between the compression setand hardness is bad.

Although, the aforesaid compositions are excellent in initial chemicalresistance, they swell extremely and cannot maintain its form in longtime dipping or dipping at 100° C. or more, because such treatment ascrosslinking is not carried out on a soft segment of the hydrogenatedblock copolymer.

SUMMARY OF THE INVENTION

A purpose of the invention is to provide a process for the preparationof a thermoplastic elastomeric resin composition which is soft andexcellent in heat deformation resistance, mechanical strength,moldability, processability, particularly, oil resistance and stainresistance.

Another purpose of the invention is to provide such a thermoplasticelastomeric resin composition.

Thus, the invention provides a process for the preparation of athermoplastic elastomeric resin composition comprising melt kneading

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a vinyl aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, and/or a hydrogenated block copolymer obtained byhydrogenating said block copolymer,

(b) 20 to 300 parts by weight of a non-aromatic softening agent forrubber,

(c) 1 to 150 parts by weight of a peroxide-crosslinking type olefinicresin and/or a copolymeric rubber containing said resin, and

(d) 10 to 150 parts by weight of a peroxide-decomposing type olefinicresin and/or a copolymer containing said resin,

characterized in that the process comprises a step of heat-processingcomponent (a), component (b), at least a part of component (c), at leasta part of component (d) and at least a part of 1.0 to 1,200 parts byweight of component (e) in the presence of an organic peroxide to causecrosslinking, wherein component (e) is at least one thermoplasticpolymer selected from the group consisting of polyester type(co)polymers, polyamide type (co)polymers and polyurethane type(co)polymers, and a subsequent step of blending these with the remainingpart of component (c), and the remaining part of component (d) andcomponent (e), if any. This process will be hereinafter referred to asprocess (P-1).

In a preferred embodiment, component (c) is one which is modified with acarboxyl, acid anhydride, epoxy or oxazolinyl group.

In another preferred embodiment, (f) 0 to 100 parts by weight of ahydrogenated petroleum resin are further blended before saidheat-processing.

In another preferred embodiment, (g) 0 to 100 parts by weight of aninorganic filler are blended in any step.

In another preferred embodiment, at least 3 parts by weight of component(d) are subjected to said heat-processing in the presence of an organicperoxide and at least 5 parts by weight of component (d) are blendedafter said heat-processing.

In another preferred embodiment, at least 1 part by weight of component(c) is subjected to said heat-processing.

In another preferred embodiment, at least 10 parts by weight ofcomponent (e) are subjected to said heat-processing.

In another preferred embodiment, the crosslinking is carried out in thepresence of a crosslinking aid which is a monomer having anethylenically unsaturated group.

In another preferred embodiment, the organic peroxide is used in anamount of 0.1 to 4.0 parts by weight.

The invention also provides a thermoplastic elastomeric resincomposition comprising

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a vinyl aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, and/or a hydrogenated block copolymer obtained byhydrogenating said block copolymer,

(b) 20 to 300 parts by weight of a non-aromatic softening agent forrubber,

(c) 1 to 150 parts by weight of a peroxide-crosslinking type olefinicresin and/or a copolymeric rubber containing said resin, and

(d) 10 to 150 parts by weight of a peroxide-decomposing type olefinicresin and/or a copolymer containing said resin,

characterized in that said composition further comprises

(e) 1.0 to 1,200 parts by weight of at least one polymer selected fromthe group consisting of polyester type (co)polymers, polyamide type(co)polymers and polyurethane type (co)polymers, and component (c) ismodified with a group which is able to react with a hydroxyl, carboxylor amino group. This composition will be hereinafter referred to ascomposition (C-1).

In a preferred embodiment, component (c) is one which is modified with acarboxyl, acid anhydride, epoxy or oxazolinyl group.

In another preferred embodiment, the composition further comprises (f) 0to 100 parts by weight of a hydrogenated petroleum resin.

In another preferred embodiment, the composition further comprises (g)at most 100 parts by weight of an inorganic filler.

In another preferred embodiment, the composition further comprises 0.1to 10 parts by weight of a crosslinking aid which is a monomer having anethylenically unsaturated group.

Another purpose of the invention is to provide a process for thepreparation of a thermoplastic elastomeric resin composition which issoft and excellent in heat deformation resistance, moldability,particularly, oil resistance and abrasion resistance, and in mechanicalproperties at high temperatures.

Further purpose of the invention is to provide such a thermoplasticelastomeric resin composition.

The present inventors have now found the following. If component (d),peroxide-decomposing type olefinic resin and/or a copolymer containingsaid resin, is melt kneaded all in step (I) which will be mentionedbelow, most of (d) is decomposed by the molecule cutting action of anorganic peroxide. Therefore, the flowability of the composition isextremely decreased and homogeneous dispersion of other components cannot be obtained. Accordingly, physical properties, such as tensileproperties, are decreased and delamination is observed in theelastomeric composition obtained. Meanwhile, if component (d) is notblended at all in step (I), the flowability of the composition is notimproved during melt kneading. Particularly, dispersion of component (a)is poor and, therefore, cross linking cannot be carried out in a gooddispersing state, which causes deterioration in physical properties suchas tensile properties or delamination in the elastomeric compositionobtained.

Meanwhile, if allocated parts of component (d) are blended and meltkneaded in steps (1) and (11), the deterioration in the physicalproperties mentioned above does not occure in the elastomericcomposition obtained, and good appearance, adjustment of hardness andshrinkage factor may be effectively achieved as envisaged by blendingcomponent (d).

Then, the invention further provides a process for the preparation of athermoplastic elastomeric resin composition comprising melt kneading

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a vinyl aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, and/or a hydrogenated block copolymer obtained byhydrogenating said block copolymer,

(b) 20 to 240 parts by weight of a non-aromatic softening agent forrubber, and

(d) 5 to 100 parts by weight of a peroxide-decomposing type olefinicresin and/or a copolymeric rubber containing said resin,

characterized in that the process comprises the following steps:

(I) melt kneading the whole amounts of components (a) and (b) and thewhole amounts of

(k) 1 to 30 parts by weight of liquid polybutadiene,

(l) 0.01 to 15 parts by weight of an unsaturated glycidyl compound orderivative thereof, and

(m) 0.01 to 15 parts by weight of an unsaturated carboxylic acid orderivative thereof, and a part of component (d), and, at the same timeor subsequently, melt kneading these with the whole of

(h) 0.1 to 3.5 parts by weight of an organic peroxide per 100 parts byweight of a total amount of components (a), (b), (d) and (k), and

(II) melt kneading the product obtained from step (I) with the remainingpart of component (d). This process will be hereinafter referred to asprocess (P-2).

In step (I) of the aforesaid present process, component (d) isdecomposed by the action of (h) organic peroxide to enhance theflowability of the composition and, at the same time, to generateradicals which crosslink component (a) by a chain reaction andalternatively react with functional groups of other components. In step(II), component (d) is homogeneously dispersed in a matrix resincomposed mainly of the crosslinked (a) to achieve the purposes of thepresent invention. Here, components (b) and (k), alone or by interactingwith each other, give softness to the elastomeric composition obtained.Components (I) and (m) behave as a modifier to enhance a compatibilizingeffect. An optional component (c) further enhances the crosslinkingeffect of component (a) under the action of (h) organic peroxide.

In a preferred embodiment, a weight ratio of the amount of component (d)blended in step (I) and that in step (II) is 10:90 to 90:10.

In another preferred embodiment, the whole of (c) at most 100 parts byweight of a peroxide-crosslinking type olefinic resin and/or acopolymeric rubber containing said resin are also melt kneaded first instep (I), where the amount of the organic peroxide (h) is 0.1 to 3.5parts by weight per 100 parts by weight of a total amount of components(a), (b), (c), (d) and (k).

In another preferred embodiment, (i) 0.1 to 3.5 parts by weight of acrosslinking aid per 100 parts by weight of a total amount of components(a), (b), (d) and (k) are kneaded together with component (h) in step(I).

The invention also provides a thermoplastic elastomeric resincomposition comprising

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a vinyl aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, and/or a hydrogenated block copolymer obtained byhydrogenating said block copolymer,

(b) 20 to 240 parts by weight of a non-aromatic softening agent forrubber, and

(d) 5 to 100 parts by weight of a peroxide-decomposing type olefinicresin and/or a copolymeric rubber containing said resin,

characterized in that said composition further comprises

(k) 1 to 30 parts by weight of liquid polybutadiene,

(l) 0.01 to 15 parts by weight of an unsaturated glycidyl compound orderivative thereof, and

(m) 0.01 to 15 parts by weight of an unsaturated carboxylic acid orderivative thereof. This composition will be hereinafter referred to ascomposition (C-2).

In a preferred embodiment, the composition further comprises

(n) 10 to 1,500 parts by weight of at least one material selected fromthe group consisting of polyester (co)polymers, polyurethane(co)polymers, polyamide (co)polymers and polymethylpentene (co)polymers.

In another preferred embodiment, the composition further comprises (c) 0to 100 parts by weight of a peroxide-crosslinking type olefinic resinand/or a copolymeric rubber containing said resin.

The present inventors have further found that when component (n) whichwill be described below is further blended, even if component (d) iskneaded all in step (I), it is possible to obtain a composition havingvarious properties which is not inferior to those of the one prepared inthe aforesaid processes (P-1 and P-2) and further to give good heatresistance to it.

The invention further provides a process for the preparation of athermoplastic elastomeric resin composition comprising melt kneading

(a) 100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a vinyl aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, and/or a hydrogenated block copolymer obtained byhydrogenating said block copolymer,

(b) 20 to 240 parts by weight of a non-aromatic softening agent forrubber, and

(d) 5 to 100 parts by weight of a peroxide-decomposing type olefinicresin and/or a copolymeric rubber containing said resin,

characterized in that the process comprises the following steps:

(I) melt kneading the whole amounts of components (a), (b) and (d) andthe whole amounts of

(k) 1 to 30 parts by weight of liquid polybutadiene,

(l) 0.01 to 15 parts by weight of an unsaturated glycidyl compound orderivative thereof, and

(m) 0.01 to 15 parts by weight of an unsaturated carboxylic acid orderivative thereof, or

the whole amounts of components (a), (b), (d), (k), (I) and (m) and thewhole or a part of

(n) 10 to 1,500 parts by weight of at least one material selected fromthe group consisting of polyester (co)polymers, polyurethane(co)polymers, polyamide (co)polymers and polymethylpentene (co)polymers,and, at the same time or subsequently, melt kneading these with thewhole of

(h) 0.1 to 3.5 parts by weight of an organic peroxide per 100 parts byweight of a total amount of components of (a), (b), (d) and (k), and

(II) further melt kneading the product obtained from step (I) with theremaining part of component (n), if any. This process will behereinafter referred to as process (P-3).

In the above process, component (n) interacts with component (k) graftedto component (a) and functional groups of components (I) and (m), suchas hydroxyl groups or carboxyl groups, to achieve the present effects.

For component (n), if use is made of a material of which melting pointis much higher than that of the matrix resin, such as polymethylpenteneor nylon-6, it is preferred to conduct the melt kneading for a longertime in order to disperse it homogeneously in the matrix resin. Suchmaterials that have a comparatively high melting point decompose withdifficulty and, therefore, do not cause deterioration in physicalproperties of the resin composition. It is rather preferred to blend andmelt knead such materials in step (I) so as to disperse themhomogeneously in the matrix resin.

Meanwhile, if, component (n) is a material of which melting point is notmush higher than that of the matrix resin, such a material decomposeeasily. Accordingly, when it is blended and melt kneaded in step (I),physical properties of the elastomeric resin composition obtained aredecreased in some cases. Preferably, a most amount of such a material isblended and melt kneaded in step (II).

In a preferred embodiment, component (n) is polymethylpentene ornylon-6, and the whole or a part of component (n) is melt kneaded instep (I) or the whole of component (n) is melt kneaded in step (II)without melt kneading component (n) in step (I).

In another preferred embodiment, a part or none of component (n) is meltkneaded in step (I) and the remaining part of component (n) is meltkneaded in step (II).

In another preferred embodiment, a part or none of component (n) is meltkneaded in step (I) and the remaining part of component (n) is meltkneaded in step (II), wherein a weight ratio of component (n) blended instep (I) and that in step (II) is 10:90 to 0:100.

In another preferred embodiment, a part or none of component (n) is meltkneaded in step (I) and the remaining part of component (n) is meltkneaded in step (II), wherein component (n) is a thermoplastic polyestertype elastomer, thermoplastic polyamide type elastomer or thermoplasticpolyurethane type elastomer.

In another preferred embodiment, (i) 0.1 to 3.5 parts by weight of acrosslinking aid per 100 parts by weight of a total amount of components(a), (b), (d) and (k) are kneaded together with component (h) in step(l).

In another preferred embodiment, the whole of (c) at most 100 parts byweight of a peroxide-crosslinking type olefinic resin and/or acopolymeric rubber containing said resin are also melt kneaded first instep (I), where the amount of the organic peroxide (h) is 0.1 to 3.5parts by weight per 100 parts by weight of a total amount of components(a), (b), (c), (d) and (k).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plan view of a test piece before being bent for evaluationof adhesive property.

FIG. 2 is a front view of a test piece before being bent for evaluationof adhesive property.

FIG. 3 is a front view of a final test piece after being bent forevaluation of adhesive property.

PREFERRED EMBODIMENTS OF THE INVENTION

Component (a), Block Copolymer

Component (a) used in the invention is a block copolymer consisting ofat least two polymeric blocks (A) composed mainly of a viny aromaticcompound and at least one polymeric block (B) composed mainly of aconjugated diene compound, or a hydrogenated block copolymer obtained byhydrogenating said block copolymer, or a mixture thereof, such as vinylaromatic compound-conjugated diene compound block copolymers having astructure, A-B-A, B-A-B-A or A-B-A-B-A, or those obtained byhydrogenating such. The block copolymer and/or the hydrogenated blockcopolymer (hereinafter referred to as (hydrogenated) block copolymer)contains 5 to 60% by weight, preferably 20 to 50% by weight, of a vinylaromatic compound. Preferably, the polymeric block A composed mainly ofa vinyl aromatic compound consists wholly of a vinyl aromatic compoundor is a copolymeric block comprising more than 50% by weight, preferablyat least 70% by weight, of a vinyl aromatic compound and an optionalcomponent such as a conjugated diene compound and/or a hydrogenatedconjugated diene compound (hereinafter referred to as (hydrogenated)conjugated diene compound). Preferably, the polymeric block B composedmainly of a (hydrogenated) conjugated diene compound is composed solelyof a (hydrogenated) conjugated diene compound or is a copolymeric blockcomprising more than 50% by weight, preferably at least 70% by weight,of a (hydrogenated) conjugated diene compound with an optional componentsuch as a vinyl aromatic compound. The vinyl compound or the(hydrogenated) conjugated diene compound may be distributed at random,in a tapered manner (i.e., a monomer content increases or decreasesalong a molecular chain), in a form of partial block or mixture thereofin the polymeric block A composed mainly of a vinyl aromatic compound orthe polymeric block B composed mainly of a (hydrogenated) conjugateddiene compound, respectively. When two or more of the polymeric block Acomposed mainly of a vinyl aromatic compound or two or more of thepolymeric block B composed mainly of a (hydrogenated) conjugated dienecompound are present, they may be same with or different from each otherin structure.

The vinyl aromatic compound to compose the (hydrogenated) blockcopolymer may be one or more selected from, for instance, styrene,α-methyl styrene, vinyl toluene and p-tert.-butyl styrene, preferablystyrene. The conjugated diene compound may be one or more selected from,for instance, butadiene, isoprene, 1,3-pentadiene, and2,3-dimethyl-1,3-butadiene, preferably butadiene and/or isoprene.

Any micro structure may be selected in the polymeric block B composedmainly of the conjugated diene compound. It is preferred that thebutadiene block has 20 to 50%, more preferably 25 to 45%, of 1,2-microstructure. In the polyisoprene block, it is preferred that 70 to 100% byweight of isoprene is in 1,4-micro structure and at lest 90% of thealiphatic double bonds derived from isoprene is hydrogenated.

A weight average molecular weight of the (hydrogenated) block copolymerwith the aforesaid structure to be used in the invention is preferably5,000 to 1,500,000, more preferably 10,000 to 550,000, further morepreferably 100,000 to 550,000, particularly 100,000 to 400,000. A numberaverage molecular weight is preferably 5,000 to 1,500,000, morepreferably 10,000 to 550,000, particularly 100,000 to 400,000. A ratioof the weight average molecular weight (Mw) to the number averagemolecular weight (Mn), Mw/Mn, is preferably 10 or less, more preferably5 or less, particularly 2 or less.

Molecule structure of the (hydrogenated) block copolymer may be linear,branched, radial or any combination thereof.

Many methods were proposed for the preparation of such block copolymers.As described, for instance, in JP Publication 40-23798/1965, blockpolymerization may be carried out using a lithium catalyst or a Zieglercatalyst in an inert solvent. The hydrogenated block copolymer may beobtained by hydrogenating the block copolymer thus obtained in thepresence of a hydrogenation catalyst in an inert solvent.

Examples of the (hydrogenated) block copolymer include SBS, SIS, SEBSand SEPS. A particularly preferred (hydrogenated) block copolymer in theinvention is a hydrogenated block copolymer with a weight averagemolecular weight of 50,000 to 550,000 which is composed of polymericblock A composed mainly of styrene and polymeric block B which iscomposed mainly of isoprene and in which 70 to 100% by weight ofisoprene has 1,4-micro structure and 90% of the aliphatic double bondsderived from isoprene is hydrogenated. More preferably, 90 to 100% byweight of isoprene has 1,4-micro structure in the aforesaid hydrogenatedblock copolymer.

Component (b), Non-Aromatic Softening Agent for Rubber

Non-aromatic mineral oils and non-aromatic liquid or low molecularweight synthetic softening agents may be used as component (b) of theinvention. Mineral oil softening agents used for rubber are mixtures ofaromatic cyclic ones, napththenic cyclic ones and paraffinic ones. Thosein which 50% or more of the whole carbon atoms is in paraffinic chainsare called a paraffinic type; those in which 30 to 40% of the wholecarbon atoms is in naphthenic rings are called a naphthenic type; andthose in which 30% or more of the whole carbon atoms is in aromaticrings are called an aromatic type.

Mineral oil softening agents for rubber to be used as component (b)according to the invention are of the aforesaid paraffinic or naphthenictype. Aromatic softening agents are improper, because they makecomponent (a) soluble and hinder the crosslinking reaction so thatphysical properties of a composition obtained are not improved.Paraffinic ones are preferred as component (b). Among the paraffinicones, those with a less content of aromatic cyclic components areparticularly preferred.

The non-aromatic softening agents for rubber have a kinetic viscosity at37.8° C. of 20 to 500 cSt, a pour point of −10 to −15° C. and a flashpoint (COC) of 170 to 300° C.

In process P-1 and composition C-1, component (b) is blended in anamount of 20 to 300 parts by weight, preferably 40 to 300 parts byweight, more preferably 80 to 200 parts by weight, most preferably 100to 170 parts by weight, per 100 parts by weight of component (a). Inprocesses P-2 and P-3 and composition C-2, component (b) is blended inan amount of at most 240 parts by weight, preferably at most 200 partsby weight, more preferably at most 150 parts by weight, and at least 20parts by weight, preferably 80 parts by weight, more preferably at least100 parts by weight, per 100 parts by weight of component (a). In theseprocesses, if component (b) is used in an amount more than the upperlimit, bleed-out of the softening agent tends to take place, a finalproduct might be sticky, and mechanical properties are deteriorated. Inprocess P-1 and composition C-1, if it is used in an amount of less than20 parts by weight, moldability of the composition is lost. In processesP-2 and 3 and composition C-2, if it is used in an amount less than 20parts by weight, there is no problem in practice, but a load to theextruder increases during the process and molecule cutting occurs due toexothermic shearing. The softness of the composition deteriorates, too.

In process P-1, a part of component (b) may be blended after the heatprocessing in the presence of a peroxide, but this may cause bleed-out.Component (b) preferably has a weight average molecular weight of 100 to2,000.

Component (c), Peroxide-Crosslinking Type Olefinic Resin or aCopolymeric Rubber Containing the Same

As component (c) of the invention, use may be made of those which cause,mainly, cross-linking by being heat-treated in the presence of peroxideso that its flowability decreases. Examples of such include polyethylenehaving a polymer density of 0.88 to 0.94 g/cm³, for instance, highdensity polyethylene (polyethylene prepared in a low pressure method),low density polyethylene (polyethylene prepared in a high pressuremethod), linear low density polyethylene (copolymers of ethylene with asmaller amount of α-olefin such as butene-1, hexene-1 or octene-1) andultra-low density polyethylene; olefinic copolymers such asethylene-propylene copolymer, ethylene-vinyl acetate copolymer,ethylene-acrylate copolymer, and amorphous random copolymeric elastomerscomposed mainly of olefins such as ethylene-propylene copolymeric rubberand ehtylene-proplyrene-non-conjugated diene copolyemeric rubber.

These may be modified with a group which is able to react with ahydroxyl, carboxyl or amino group. The modified (co)polymers arepreferable in process P-1. The modification is essential in compositionC-1. Examples of such include (co)polymers modified with, for example,maleic anhydride, glycidyl methacrylate, allylglycidylether, oxazolylmethacrylate, allyloxazolylether, carboxylmethacrylate andallylcarboxylether, and polymethylmethacrylate graft copolymers.

In process P-1 and composition C-1, modified polyethylene and modifiedethylene-propylene copolymeric rubber are preferred. When polyester typepolymer is used as component (e), glycidyl methacrylate copolymers areparticularly preferred, while when polyamide type copolymer is used ascomponent (e), ethylene-glycidyl methacrylate copolymers modified withmaleic anhydride are particularly preferred. In these cases, propercrosslinked structure and compatibility may be obtained. In process P-1and composition C-1, because functional groups of a principal chain of aperoxide-crosslinking type modified olefinic polymer interact withcomponent (e), improvement in tensile properties may be effected. In thepresent invention, delamination on the surface of a molded article doesnot occur.

In processes P-2 and P-3 and composition C-2, preference is given to anethylene-octene copolymer having a density of at most 0.90 g/cm³ andethylene-hexene copolymer having a density of at least 0.90 g/cm³ whichare prepared using a metallocene catalyst (single site catalyst). WhenTm of these copolymer is not higher than 100° C., it is necessary to addand crosslink them by the time of crosslinking at the latest. Tmdisappears by the crosslinking and, therefore, fusion of octene orhexene does not occur. If the addition of them is carried out after thecrosslinking, fusion at 30 to 60° C. of octene or hexene remains and,therefore, the heat resistance is decreased.

In processes P-2 and 3 and composition C-2, one example of component (c)is an olefinic polymer which is prepared using a catalyst for olefinepolymerization which is prepared in accordance with the method describedin Japanese Patent Application Laid-Open Sho-61-296008 and which iscomposed of a carrier and a reaction product of metallocene having atleast one metal selected from the 4b group, 5b group and 6b group in theperiodic table with alumoxane, the reaction product being formed in thepresence of the carrier.

Another example of component (c) is an olefinic polymer prepared using ametal coordinated complex described in Japanese Patent ApplicationLaid-Open Hei-3-163088, which metal coordinated complex contains a metalselected from the group 3 (except scandium), groups 4 to 10 and thelanthanoid group and a delocalized π-bonding part substituted by aconstrained inducing part, and is characterized in that said complex hasa constrained geometrical form around said metal atom, and a metal anglebetween a center of the delocalized substituted π-bonding part and acenter of at least one remaining substituted part is less than that in acomparative complex which is different from it only in that aconstrained inducing substituted part is substituted with a hydrogen,and wherein in each complex having further at least one delocalizedsubstituted π-bonding part, only one, per metal atom, of the delocalizedsubstituted π-bonding parts is cyclic.

When component (c) is rubber, its Mooney viscosity, ML1+4 (100° C.), ispreferably 10 to 120, more preferably 40 to 100. If rubber with a Mooneyviscosity less than 10 is used, rubber properties of the elastomercomposition obtained are deteriorated. If rubber with a Mooney viscositymore than 120, moldability is deteriorated and, particularly, appearanceof a molded article is deteriorated.

An ethylene content in the copolymer is properly 5 to 50% by weight,preferably 6 to 20% by weight, more preferably 10 to 15% by weight. Ifthe ethylene content is less than 5% by weight, softness of theelastomer composition obtained is insufficient. If it is larger than 50%by weight, mechanical strength is deteriorated.

The peroxide-crosslinking type olefinic resin or the copolymercontaining the same preferably has a weight average molecular weight of50,000 to 1,000,000, more preferably 70,000 to 500,000. If it is lessthan 50,000, rubber properties of the elastomer composition obtained aredeteriorated. If it exceeds 1,000,000, moldability is deteriorated and,particularly, appearance of a molded article is deteriorated.

In process P-1 and composition C-1, component (c) is blended in anamount of 1 to 150 party by weight, preferably 3 to 50 parts by weight,per 100 parts by weight of component (a). If the amount is less than 1part by weight, compatibility in the composition obtained isinsufficient and, therefore, mechanical properties are deteriorated. Ifit exceeds 150 parts by weight, compression set of the elastomercomposition obtained are deteriorated. In process P-1, preferably, atleast 1 part by weight of component (c) is blended before the heattreatment in the presence of peroxide.

In processes P-2 and 3 and the composition C-2, an MFR determined at190° C. and a load of 2.16 kg is preferably 0.1 to 10.0 g/10 min., morepreferably 0.3 to 5.0 g/10 min. Component (c) is blended in an amount ofat most 100 parts by weight, preferably at most 50 parts by weight, andpreferably at least 5 parts by weight, per 100 parts by weight ofcomponent (a). If the upper limit is not kept, softness of the elastomercomposition obtained is lost and bleedout of softening agent (b) occurseasily.

Component (d), Peroxide-Decomposing Type Olefinic Resin or a CopolymerContaining the Same

First, component (d) in process P-1 and composition C-1 will bedescribed. Component (d) attains an effect of improving dispersion ofthe rubber in the composition obtained so as to improve appearance of amolded article. Component (d) is blended in an amount of 10 to 150 partsby weight, preferably 25 to 100 parts by weight, per 100 parts by weightof component (a). If the amount is less than 10 parts by weight,moldability of the elastomer composition obtained is deteriorated. If itexceeds 150 parts by weight, softness and rubber elasticity of theelastomer composition are deteriorated.

A peroxide-decomposing type olefinic resin suitable as component (d) ofthe invention has at least 20% of rrrr/l-mmmm in a pentad ratio in a¹³C-nuclear magnetic resonance method and a fusion peak temperature (Tm)of at least 150° C., preferably 150 to 167° C., and fusion enthalpy(ΔHm) of at most 100 J/g, preferably 25 to 83 mJ/mg, as determined bydifferential scanning calorimetry (DSC). Crystallinity may be estimatedfrom Tm and ΔHm. If Tm and ΔHm are out of the aforesaid ranges, rubberelasticity at 100° C. or higher of the elastomer composition obtained isnot improved.

It is preferred to use two types of peroxdie-decomposing type olefinicresins in combination as will be described below.

Peroxide-decomposing type olefinic resins to be blended before thecrosslinking reaction are preferably high molecular weight propylenehomopolymers such as isotactic polypropylenes, or copolymers ofpropylene with a smaller amount of other α-olefine such as ethylene,1-butene, 1-hexene or 4-methyl-1-pentene. These resins preferably havean MFR (ASTM D-1238, Condition L, 230° C.) of 0.1 to 10 g/l 0 min., morepreferably 3 to 8 g/l 0 min.

Peroxide-decomposing type olefinic resins to be blended after thecrosslinking reaction are preferably one or more of highly flowableblock or random propylene copolymers or homopolymers, such as isotacticpolypropylenes or copolymers of propylene with a smaller amount of otherα-olefine such as ethylene, 1-butene, 1-hexene or 4-methyl-1-pentene.These resins preferably have an MFR of 5 to 200 g/10 min., morepreferably 8 to 150 g/10 min., particularly 10 to 100 g/10 min.

If the MFR of the peroxide-decomposing type olefinic resin to be blendedbefore the crosslinking reaction is less than 0.1 g/10 min., moldabilityof the elastomer composition obtained is deteriorated. If it exceeds 10g/10 min., rubber elasticity of the elastomer composition obtained isdeteriorated.

If the MFR of the peroxide-decomposing type olefinic resin to be blendedafter the crosslinking reaction is less than 5 g/10 min., moldability ofthe elastomer composition obtained is deteriorated. If it exceeds 200g/10 min., rubber elasticity of a composition obtained is deteriorated.

In addition to those described above, use may be made of aperoxide-decomposing type olefinic resin composed of boilingheptane-soluble polypropylene having a number average molecular weight(Mn) of at least 25,000 and a ratio of Mw to Mn, Mw/Mn, of at most 7 andboiling heptane-insoluble polypropylene having a melt index of 0.1 to 4g/10 min. or a peroxide-decomposing type olefinic resin composed ofboiling heptane-soluble polypropylene having an intrinsic viscosity [η]of at least 1.2 dl/g and boiling heptane-insoluble polypropylene havingan intrinsic viscosity [η] of 0.5 to 9.0 dl/g.

According to the invention, at least a part of component (d), preferablyat least 3 parts by weight of component (d), is subjected to the heattreatment in the presence of an organic peroxide, and the remaining partof component (d), preferably at least 5 parts by weight of (d), isblended after the heat treatment. All components are dispersed uniformlyby such portionwise addition of component (d), so that stickiness on thesurface of a molded article disappears and moldability is also improved.

It is preferred that the amount of component (d) to be blended beforethe crosslinking reaction (X) is less than that after the crosslinkingreaction (Y), because the resin composition will have better rubberelasticity. The aforesaid X and Y may be determined depending upon afinal molding process, such as injection molding or extrusion molding,in a specific case.

Second, component (d) in processes P-2 and P-3 and composition C-2 willbe described. Component (d) of the invention again attains an effect ofimproving dispersion of the rubber in the composition obtained so as toimprove appearance of a molded article. In addition, component (d)exhibits an effect of adjusting hardness and shrinkage. The component isan olefinic (co)polymer which is pyrolyzed by the heat treatment in thepresence of peroxide to decrease its molecular weight and, therefore,its melting flowability increases. Examples of such include isotacticpolypropylenes, and copolymers of propylene with other α-olefine such asethylene, 1-butene, 1-hexene or 4-methyl-1-pentene.

A peroxide-decomposition type olefinic resin suitable as component (d)of the invention has Tm of 150 to 167° C. and ΔHm of 25 to 83 mJ/mg, asdetermined by DSC on its homopolymeric part. Crystallinity may beestimated from Tm and ΔHm. If Tm and ΔHm are out of the aforesaidranges, rubber elasticity at 100° C. or higher of the elastomercomposition obtained is not improved.

Component (d) has an MFR (ASTM D-1238, Condition L, 230° C.) ofpreferably 0.1 to 50 g/10 min., more preferably 0.5 to 20 g/10 min. Ifthe MFR is less than 0.1 g/10 min., moldability of the elastomercomposition obtained deteriorates. If it exceeds 50 g/10 min., rubberelasticity of the elastomer composition obtained deteriorates.

Component (d) is blended in an amount of at most 100 parts by weight,preferably at most 50 parts by weight, and at least 5 parts by weight,preferably at least 10 parts by weight, per 100 parts by weight ofcomponent (a). If the amount is less than the lower limit, moldabilityis deteriorated. If it exceeds the upper limit, the elastomercomposition obtained is too hard and lacks softness, so that it isdifficult to obtain an article with rubber-like touch.

Component (e), Polyester Type (Co)Polymer, Polyamide Type (Co)Polymer orPolyurethane Type (Co)Polymer

The polyester type (co)polymer, polyamide type (co)polymer orpolyurethane type (co)polymer is not restricted to particular one andany polymer and copolymer may be used satisfactorily. The copolymers maybe a block or graft copolymer. The (co)polymers are preferred to haveelastomeric properties. Commercially available polymers may be usedsatisfactorily. The aforesaid copolymers are particularly preferred. Theaforesaid (co)polymers may be used alone or in a combination. Examplesof the polyester type (co)polymer include (co)polymers in which a hardcomponent is an aromatic polyester and a soft component is an aliphaticpolyether, or in which a hard component is an aromatic polyester and asoft component is an aliphatic polyester, or in which a hard componentis polybutylene naphthalate and a soft component is an aliphaticpolyether. Examples of the polyamide type (co)polymer include nylon-6,nylon-6,6, nylon-4,6, nylon-6,10, nylon-6,12, and block elastomers inwhich a hard component is polyamide (nylon-6 type or nylon-12 typepolyamide is used as polyamide) and a soft component is polyetherester,or a hard component is polyamide and soft component is polyetherester.Examples of the polyurethane type (co)polymer include lactone type,ester type or ether type (co)polymers.

Component (e) is blended in an amount of 1.0 to 1,200 parts by weight,preferably 100 to 500 parts by weight, per 100 parts by weight ofcomponent (a). If the amount is more than 1,200 parts by weight,softness of the elastomer composition obtained is decreased to be littledifferent from that of polyester type (co)polymer, polyamide type(co)polymer or polyurethane type (co)polymer.

In the present invention, the addition of component (e) makes theelastomer composition extremely improved in oil resistance and stainresistance.

Component (f), Hydrogenated Petroleum Resin

A hydrogenated petroleum resin may be blended in the invention, ifneeded. When the hydrogenated petroleum resin is blended, there may beobtained such effects of balancing softness and stickiness. That is,softness is attained without stickiness. Examples of the hydrogenatedpetroleum resin include hydrogenated aliphatic petroleum resins,hydrogenated aromatic petroleum resins, hydrogenated copolymer petroleumresins, hydrogenated alicyclic petroleum resins and hydrogenated terpeneresins.

The hydrognated petroleum resins may be obtained by hydrogenating, in aconventional manner, petroleum resins produced in conventionalprocesses.

The petroleum resin used herein refers to resineous substances obtainedin various processes in the refining industry and the petrochemicalindustry, or resins obtained by copolymerizing unsaturated hydrocarbonsrecovered from such processes, particularly from a naphtha crackingprocess, for instance, aromatic petroleum resins composed mainly of a C₅fraction, aromatic petroleum resins composed mainly of a C₉ fraction,copolymeric petroleum resins from those, and alicyclic petroleum resins.

A preferred hydrogenated petroleum resin is a hydrogenated alicyclicpetroleum resin, particularly, such obtained by copolymerizingcyclopentadiene type compounds with vinyl aromatic compounds andhydrogenating the copolymer obtained.

The hydrogenated petroleum resin used in the invention is preferably onewhich is completely hydrogenated. Partially hydrogenated ones tend togive worse stability and resistance to weathering.

The hydrogenated petroleum resin is blended in an amount of 100 parts byweight or less, per 100 parts by weight of component (a). Even if theamount exceeds 100 parts by weight, a further softening effect on thecomposition obtained is little and, rather, an action of the petroleumresin as a tackifier becomes conspicuous and mechanical propertiesbecome worse as well. If a non-hydrogenated petroleum resin is used,heat stability of the composition obtained is bad, so that the purposeof the invention is not attained.

Component (g), Inorganic Filler

Inorganic fillers may be blended, if needed. The fillers improve somephysical properties, such as a permanent compressive strain of a moldedarticle, and further offer an economical advantage as an extender. Anyconventional inorganic fillers may be used, such as calcium carbonate,talc, magnesium hydroxide, mica, clay, barium sulfate, natural silica,synthetic silica (white carbon), titanium oxide, and carbon black. Amongthose, calcium carbonate and talc are particularly preferred.

The inorganic filler may be blended in an mount of 0 to 100 parts byweight, preferably 0 to 60 parts by weight, per 100 parts by weight ofcomponent (a). If the amount exceeds 100 parts by weight, mechanicalstrength of an elastomer composition obtained is very low and, further,its hardness is so high that its flexibility is lost and an article withrubber-like touch cannot be obtained.

Component (h), Organic Peroxide

An organic peroxide decomposes component (d) to increase flowability ofthe composition during melt kneading and, therefore, makes dispersion ofa rubber component good. At the same time, it generates radicals whichchain react to crosslink component (a). In addition, it accelerates thecrosslinking of component (a) by optional component (c). Examples of theorganic peroxides used in the invention include dicumyl peroxide,di-tert.-butyl peroxide, 2,5-dimethyl-2,5-di(tert.-butylperoxy) hexane,2,5-dimethyl-2,5-di(tert.-butylperoxy) hexine-3,1,3-bis(tert.-butylperoxyisopropyl) benzene,1,1-bis(tert.-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4,-bis(tert.-butylperoxy)valerate, benzoylperoxide,p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide,tert.-butylperoxy benzoate, tert.-butylperoxyisopropyl carbonate,diacetyl peroxide, lauroyl peroxide, and tert.-butylcumyl peroxide.

Among those, most preferred are2,5-dimethyl-2,5-di(tert.-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert.-butylperoxy) hexine-3 and1,3-bis(tert.-butylperoxyisopropyl)benzene in terms of smell, coloringand scorch stability.

In the process P-1 and the composition C-1, the amount of the peroxideadded is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 2.5parts by weight, particularly 0.8 to 2.5 parts by weight, per total 100parts by weight of components (a) to (g) present at the time of additionof the peroxide. If the amount is less than 0.1 parts by weight, ittends not to attain the required crosslinking, while if the amountexceeds 3.0 parts by weight, it tends to proceed with the crosslinkingtoo much to deteriorate the dispersion of the crosslinked materials.

In the processes P-2 and P-3 and the composition C-2, the amount ofcomponent (h) added is determined with consideration of the amounts ofthe aforesaid components (a) to (d) and component (k) describedhereinafter and, particularly, the quality of the thermoplasticelastomer obtained. It is blended preferably in an amount of at most 3.5parts by weight, particularly at most 2.0 parts by weight, andpreferably at least 0.1 part by weight, per total 100 parts by weight ofcomponents (a) to (d) and (k). If the amount is more than the upperlimit, the moldability becomes worse, while it is less than the lowerlimit, it tends not to attain sufficient crosslinking and, therefore,the heat resistance and mechanical strength of the elastomer obtainedbecomes worse.

Component (i), Crosslinking Aid

In the partial crosslinking treatment in the presence of the organicperoxide in the processes for the preparation of a thermoplasticelastomer composition according to the invention, a crosslinking aid maybe blended. Examples of the crosslinking aid include polyvalent vinylmonomers such as divinylbenzene, triallylcyanurate, vinyl butylate andvinyl stearate and polyvalnet methacrylate monomers such asethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate,triethylenglycol dimethacrylate, polyethylenglycol dimethacrylate,trimethylolpropane trimethacrylate and allyl methacrylate, and diallyesters of orthophthalic acid, isophthalic acid or terephthalic acid.These compounds will cause the crosslinking reaction more uniformly andmore efficiently.

In the process P-1 and the composition C-1, a combination oftriethylenegloycol dimethacrylate and diallyl phthalate is mostpreferred, because this combination is easy to handle and attains a wellcompatibility of a main component to be treated, peroxide-crosslinkingtype olefinic polymer rubber (c) with component (e), polyester typecopolymer, and this has a solubilizing action for the peroxide to act asa dispersion aid for the peroxide, so that the crosslinking action inthe heat treatment is uniform and efficient to give a cross-linkedthermoplastic elastomer with a good balance between hardness and rubberelasticity.

The amount of the crosslinking aid used in the present process P-1 andthe composition C-1 is preferably 0.1 to 10 parts by weight, morepreferably 1 to 8 parts by weight, particularly 2 to 6 parts by weight,per total 100 parts by weight of components (a) to (f) present at thetime of the addition of the crosslinking aid. It is preferred that theamount of the crosslinking aid added is about 2 to 2.5 times as large asthe amount of the peroxide added. If the amount is less than 0.1 part byweight, it tends not to attain the crosslinking needed, while if itexceeds 10 parts by weight, it tends to decrease the crosslinkingeffect.

In the processes P-2 and P-3 and the composition C-2, triethylenegloycoldimethacrylate is most preferred. This compound is easy to handle andwell compatible with main components to be treated, components (a), and(c), and this has a solubilizing action for the peroxide to act as adispersion aid for the peroxide, so that the crosslinking action in theheat treatment is uniform and efficient to give a cross-linkedthermoplastic elastomer with a good balance between hardness and rubberelasticity.

In the processes P-2 and P-3 and the composition C-2, the amount of thecrosslinking aid blended is determined with consideration of the amountsof the aforesaid components (a) to (d) and component (k) describedhereinafter and the quality of the thermoplastic elastomer obtained. Itis blended preferably in an amount of at most 3.5 parts by weight,particularly at most 2.5 parts by weight, and preferably at least 0.1part by weight, per total 100 parts by weight of components (a) to (d)and (k). If the amount is more than the upper limit, a degree ofcrosslinking tends to decrease because of self polymerization, while itis less than the lower limit, it tends not to attain the effect of thismaterial sufficiently.

Component (j), Antioxidant

Antioxidant may also be added, if needed, such as phenolic antioxidantsuch as 2,6-di-tert.-butyl-p-cresol, 2,6-di-tert.-butylphenol,2,4-di-methyl-6-tert.-butylphenol, 4,4-dihydroxydiphenyl, andtris(2-methyl-4-hydroxy-5-tert.-butylphenyl)butane, phosphite typeantioxidants and thioether type antioxidants. Among those, the phenolicantioxidants and the phosphite type antioxidants are preferred.

In the processes P-1 and the composition C-1, the amount of theantioxidant is preferably 3 parts by weight or less, more preferably 1part by weight or less, per total 100 parts by weight of components (a)to (f) present at the time of the addition of the antioxidant. It ispreferred to add the antioxidant in the first step of the preparationprocess so as to prevent hydrolysis of the polyester type thermoplasticelastomer such as TPEE.

In the processes P-2 and P-3 and the composition C-2, the amount of theantioxidant is preferably 3 parts by weight or less, more preferably 1part by weight or less, per total 100 parts by weight of components (a)to (d) and component (k) described below.

Component (k), Liquid Polybutadiene

Liquid polybutadiene is a polymer in which microstructure of a mainchain is composed of vinyl 1,2-bonding, trans 1,4-bonding and cis1,4-bonding and which is transparent liquid in room temperature. Thevinyl 1,2-bonding amounts to preferably 30% by weight or less. If thevinyl 1,2-bonding exceeds 30% by weight, the properties of thecomposition obtained tends to deteriorate.

A number average molecular weight of the liquid polybutadiene ispreferably at most 5,000, more preferably at most 4,000, and preferablyat least 1,000, more preferably at least 3,000. If the number averagemolecular weight is below 1,000, the heat deformation resistance of thecomposition obtained tends to become worse, while if it exceeds 5,000,the compatibility of the composition obtained tends to become worse.

The liquid polybutadiene is preferably a copolymerizable compound havingone or more groups selected from epoxy, hydroxyl, isocianate andcarboxyl groups. Among these, one having a hydroxyl group and acopolymerizable unsaturated double bond is particularly preferred.Commercially available liquid polybutadiene includes, for example,R-45HT, trade mark, ex Idemitsu Petrochemical Co.

Component (k) is blended in an amount of at most 30 parts by weight,preferably at most 10 parts by weight, and at least 1 part by weight,preferably at least 3 parts by weight, per 100 parts by weight ofcomponent (a). If the amount is below the lower limit, effects of theaddition is not observed, while if it exceeds the upper limit, themechanical properties of the composition is deteriorated.

Component (I), Unsaturated Glycidyl Compound or Derivative Thereof

An unsaturated glycidyl compound or derivative thereof is used as amodifier. As the unsaturated glycidyl compound or derivative thereof,use may be made preferably of glycidyl compounds having an unsaturatedgroup which may copolymerize with olefin and a glycidyl group in themolecule, more preferably, glycidyl methacrylate. Preferably,polyethylene and polypropylene are modified by this modifier. That is, asoft component of component (a), hydrogenated block copolymer, component(c), peroxide-crosslinking type olefinic resin and/or a copolymericrubber and component (d), peroxide-decomposing type olefinic resinand/or a copolymeric rubber containing said resin, are modified.

Component (l) is blended in an amount of at most 15 parts by weight,preferably at most 10 parts by weight, and at least 0.01 part by weight,preferably at least 0.1 part by weight, more preferably at least 3 partsby weight, per 100 parts by weight of component (a). If the amountexceeds the upper limit, heat deformation resistance and mechanicalproperties of the composition are deteriorated and, in addition, theeffect of improving compatibility of component (n), if blended, is notobserved.

Component (m), Unsaturated Carboxylic Acid or Derivative Thereof

An unsaturated carboxylic acid or derivative thereof is used as amodifier. Preferably, examples of the unsaturated carboxylic acid orderivative thereof include acrylic acid, methacrylic acid, maleic acid,dicarboxylic acid or derivatives thereof such as acids, halides, amides,imides, anhydrides or esters. Particularly, maleic anhydride (MAH) ispreferably used. Preferably, polypropylene is modified by this modifier.That is, it is considered that a soft component of component (a),hydrogenated block copolymer, and component (d), peroxide-decomposingtype olefinic resin and/or a copolymeric rubber containing said resin,are modified.

Component (m) is blended in an amount of at most 15 parts by weight,preferably at most 10 parts by weight, and at least 0.01 part by weight,preferably at least 0.1 part by weight, more preferably at least 5 partsby weight, per 100 parts by weight of component (a). If the amountexceeds the upper limit, conspicuous yellowing occurs in the compositionand heat deformation resistance and mechanical properties of thecomposition deteriorate and, in addition, the effect of improvingcompatibility of component (n), if blended, is not observed.

Component (n), Polyester (co)polymer, Polyurethane (co)polymer,Polyamide (co)polymer and Polymethylpentene (co)polymer

A polyester (co)polymer, polyurethane (co)polymer, polyamide (co)polymeror polymethylpentene (co)polymer is not restricted to particular one andany (co)polymers may be used satisfactorily. Preferably, block copolymeror graft copolymer is used. It preferably has elastomeric properties. Asthis component, commercially available products may be used.

The aforesaid (co)polymers may be used alone or as a combination ofthem. Examples of the polyester (co)polymer include (co)polymers inwhich a hard component is an aromatic polyester and a soft component isan aliphatic polyether, or in which a hard component is an aromaticpolyester and a soft component is an aliphatic polyester, or in which ahard component is polybutylene naphthalate and a soft component is analiphatic polyether. Examples of the polyamide (co)polymer includenylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-6,12, or blockelastomers in which a hard component is polyamide (nylon-6 type ornylon-12 type polyamide is used as polyamide) and a soft component ispolyetherester. Examples of the polyurethane (co)polymer include lactonetype, ester type or ether type (co)polymers. Examples of thepolymethylpentene (co)polymer include poly-4-methylpentene-1.

Component (n) is blended in an amount of at most 1,500 parts by weight,preferably at most 1,200 parts by weight, and at least 20 parts byweight, preferably at least 100 parts by weight, per 100 parts by weightof component (a). If the amount exceeds the upper limit, softness of theelastomer composition obtained is decreased, which becomes to be littledifferent from that of polyester (co)polymer, polyamide (co)polymer,polyurethane (co)polymer or polymethylpentene(co)polymer. The additionof component (n) may extremely improve the oil resistance, abrasionresistance and properties at a high temperature such as tensileproperties at a high temperature of the elastomer composition obtained.

It is possible for the compositions according to the invention tocontain various additives such as anti-blocking agents, sealingproperty-improving agents, heat stabilizers, UV absorbers, lubricants,nucleating agents and colorants in addition to the aforesaid components,depending on the applications.

The process P-1 will be described below.

The heat processing in the presence of an organic peroxide and theblending in the process for the preparation of the resin compositionaccording to the invention may be carried out by any conventional means.The process of the invention may be carried out, for instance, in thefollowing three steps.

In a first step, component (a), component (b), at least a part ofcomponent (c), at least a part of component (d) and at least a part ofcomponent (e) are melt and kneaded, optionally together with component(f), optional additives such as an antioxidant, a light stabilizer, acolorant and a flame retardant, and component (g).

Any conventional means for kneading rubbers or plastics may be usedsatisfactorily, such as single screw extruders, twin screws extruders,rolls, Banbury mixers, and various kneaders. In this step, a compositionis obtained in which all of those components are dispersed uniformly.

In a second step, a peroxide and, if desired, a crosslinking aid areadded to the composition obtained in the first step, and further kneadedunder heating to cause crosslinking. Particularly good properties areattained in this way, i.e., by previously melt kneading components (a)to (g) to have microdispersion and then adding an organic peroxide tocause crosslinking. This step may be carried out, for instance, by twinscrews extruders or Banbury mixers.

The aforesaid first and second steps may be joined in a single stepwhere the components are mixed and melt kneaded.

In a third step, the remaining part of component (c) and the remainingpart of component (d) and the remaining part of component (e), if any,are added and kneaded. The kneading may be carried out, for instance, bysingle screw extruders, twin screws extruders, rolls, Banbury mixers, orvarious kneaders. In this step, dispersion of each component proceedsfurther and, at the same time, the reaction is completed.

A twin screws extruder with a LID ratio of 47 or more or a Banbury mixeris preferred as a kneading means, because all of the steps may becarried out continuously. For instance, when a twin screws extruder isoperated at a screw rotation speed of 80 to 250 rpm, preferably 80 to100 rpm, each component is dispersed well to give good properties.

A kneading temperature in the first step is preferably set so that eachcomponent melts completely to be easily mixed. A kneading temperature inthe second step is preferably chosen so that a sufficient shearing forceacts on the organic peroxide and the other components and, further, thereaction proceeds uniformly. In the third step, the temperature isdesirably set so that the mixing of all of the components proceedsfurther and the reaction is completed.

Component (a) shall be added in the first step or, at the latest, in thesecond step, whereby a part of component (a) causes a crosslinkingreaction to better the dispersion of each components.

Component (b) and component (f) is preferably blended in the first step.If they are blended in the third step, it will be a cause for bleed-out,stickiness or deterioration in properties.

Component (c) may be blended all in the first step. However, a properamount of it may be blended in the first step and the remaining part ofit may be blended in the second or third step to adjust theprocessability, flowability and mechanical strength. This is preferredwhen component (e) is blended in the third step, because the compositionpartially crosslinked in the presence of the peroxide is compatible witha part of component (c) added in the second or third step and comes intomicrodispersion, so that physical properties of the elastomercomposition obtained, such as mechanical strength, are improved. In thecase where component (e) is not blended in the third step, it ispreferred that a proper amount of component (c) is blended in the firststep.

As mentioned above, a proper part of component (d) is blended in thefirst step and the remaining part is blended in the third step, wherebythe remaining part of component (d) added in the third step iscompatible with the composition which was partially cross-linked in thepresence of a peroxide and comes into microdispersion, so that physicalproperties of the elastomer composition obtained, such as moldability,flowability and mechanical strength, are improved. The inorganic fillermay be blended in either or both of the first step and the third step.

A degree of the crosslinking of the thermoplastic elastomer compositionthus obtained is represented by a gel ratio and a dynamic elasticity.The gel ratio is determined as follows: 1 g of a sample is wrapped witha 100 mesh wire netting and extracted in boiling xylene in a Soxhletextractor for 10 hours. A ratio of the weight of the remaining solid tothe weight of the sample is the gel ratio. The dynamic elasticity isrepresented by a storage modulus of melt viscoelasticity determined byparallel plates.

The degree of the crosslinking is preferably such represented by a gelratio of 30 to 45% by weight, more preferably 35 to 45% by weight, and astorage modulus of 10⁵ to 10⁷ Pa. Below these ranges, the compressionset and oil resistance of the thermoplastic elastomer compositionobtained are bad. Above these ranges, softness is lost and moldabilityand processability are bad, and also, tensile properties aredeteriorated.

Each component is micro-dispersed more uniformly in the thermoplasticelastomer composition thus obtained, compared to compositions of theprior art. Accordingly, compression set, tensile strength and otherphysical properties are steadily attained.

The processes P-2 and P-3 will be described below.

The process for the preparation of the resin composition according tothe invention comprises the following steps:

(I) melt kneading, in advance, the whole amounts of components (a), (b),(k), (l) and (m) and component (c), if used, and a part of component(d), and at the same time or subsequently, melt kneading these with thewhole of component (h), and

(II) melt kneading the product obtained from step (I) with the remainingpart of component (d).

In this process, component (d) is melt kneaded partially in step (I) andpartially in step (II). The ratio of component (d) blended in step (l)to that in step (II) is preferably 10:90 to 90:10 in weight ratio. Ifthe amount of (d) melt kneaded in step (I) is too much, a large part of(d) is decomposed by the molecule-cutting action of an organic peroxide,so that flowability of the composition is considerably decreased and,therefore, uniform dispersion of each component may not be obtained, anddeterioration in physical properties such as tensile properties andsurface peeling occur in the composition obtained. Meanwhile, the amountof (d) melt kneaded in step (I) is too little, flowability of thecomposition is not improved during the melt kneading. Particularly,dispersion of (a) is deteriorated and, therefore, the crosslinkingcannot be carried out in a good dispersing state, so that deteriorationin physical properties such as tensile properties and surface peelingoccur in the composition obtained.

If the aforesaid component (i), crosslinking aid, is used, it is meltkneaded together with component (h), organic peroxide, in step (I),whereby the effects of component (i) may be attained.

A preferred embodiment of the present process will be described below.For example, the whole amounts of components (a), (b), (k), (l) and (m)and component (c), if used, and a part of component (d) are meltkneaded, together with optional additives such as an antioxidant, alight stabilizer, a pigment and a flame retardant. The means for meltkneading are not restricted to particular ones and any conventionalmeans may be used, such as single screw extruders, twin screwsextruders, rolls, Banbury mixers, and various kneaders. A melt kneadingtemperature is preferably 160 to 180° C. Next, component (h) andpreferably component (i) are added to the product obtained by this meltkneading and melt kneaded together, whereby partial crosslinking ofcomponent (a) by components (d) and (c) may be attained. The meltkneading may be carried out generally on, for example, twin screwsextruders or Banbury mixers. Subsequently, the remaining part ofcomponent (d) is further added to the product obtained by this meltkneading and melt kneaded. A melt kneading temperature for crosslinkingis preferably 180 to 240° C., more preferably 180 to 220° C. This meltkneading may be carried out using, for example, single screw extruders,twin screws extruders, rolls, Banbury mixers, and various kneaders. Forexample, when a twin screws extruder with an L/D ratio of 47 or more ora Banbury mixer is used, it is possible to carry out the aforesaidprocess continuously.

In the case where component (n) is blended and melt kneaded, theelastomer composition according to the invention may be prepared in thefollowing process.

That is, the process comprises the following steps:

(I) melt kneading, in advance, the whole amounts of components (a), (b),(d), (k), (l) and (m) and, if used, component (c) or the whole amountsof components (a), (b), (d), (k), (l) and (m) and, if used, component(c) and the whole or a part of component (n) and, at the same time orsubsequently, melt kneading these with the whole of (h), and

(II) further melt kneading the product obtained from the step (I) withthe remaining part of component (n), if any.

For materials used as component (n), those having a melting point muchhigher than that of a matrix resin, such as nylon-6 andpolymethylpentene may be blended and melt kneaded all in step (I), orthe whole of them may be blended and melt kneaded in step (II), or theymay be blended and melt kneaded partly in step (I) and partly in step(II) in a proper ratio. Such materials are preferably melt kneaded for along time in order to disperse them uniformly in a matrix resin. Inaddition, such materials are decomposed with difficulty, and therefore,give no deterioration in properties of the resin composition as a resultof the decomposition in step (I). Accordingly, it is preferred to blendand melt knead these materials in step (I) and to disperse themuniformly in the matrix resin. In the case where they are blended instep (II), it is preferred that these materials are sufficiently meltedat a high temperature in advance and then side fed and kneaded.

For materials used as component (n), those having a relatively lowmelting point, such as thermoplastic polyester type (co)polymers,thermoplastic polyamide type (co)polymers or thermoplastic polyurethanetype (co)polymers, are preferrably blended and melt kneaded separetelyin steps (I) and (II), with a ratio of the weight in step (I) to theweight in (II) being 10:90 to 0:100. Particularly preferred is a processin which none of them is blended in step (I) and the whole of them isblended and melt kneaded in step (II). If the amount of them blended instep (I) exceeds the upper limit, the decomposition of them may resultsin deterioration in physical properties of the elastomer compositionobtained in some cases.

In the case where component (i), crosslinking aid, is used, component(i) is blended and melt kneaded in step (I) together with component (h),organic peroxide.

An embodiment of the present process will be described below. Forexample, the whole amounts of components (a), (b), (d), (k), (l) and (m)and, if used, component (c) are blended optionally with a part ofcomponent (n), and an antioxidant, a light stabilizer, a pigment and aflame retardant, if desired, and melt kneaded. Means for melt kneadingare not restricted to particular ones and any conventional means may beused, such as single screw extruders, twin screws extruders, rolls,Banbury mixers, and various kneaders. A melt kneading temperature ispreferably 160 to 220° C. To the product obtained by the melt kneadingare then added and melt kneaded component (h) and preferably component(i), whereby the crosslinking of component (a) by component (d) andcomponent (c), if any, may be attained. The melt kneading is carried outon, for example, a twin screws extruder or a Banbury mixer.Subsequently, the remaining part of component (n) is further added tothe product obtained by the melt kneading, followed by melt kneading. Amelt kneading temperature is preferably 180 to 240° C., particularly 180to 220° C. This melt kneading may be carried out using, for example,single screw extruders, twin screws extruders, rolls, Banbury mixers,and various kneaders. For example, when a twin screws extruder with anL/D ratio of 47 or more or a Banbury mixer is used, it is possible tocarry out the aforesaid process continuously. The melt kneading in alatter stage corresponding to step (II) may also be carried out, forexample, immediately before an injection molding.

A degree of the crosslinking of the thermoplastic elastomer compositionthus obtained is represented by a gel ratio and a storage modulus. Thegel ratio is determined as mentioned above. The storage modulus isdetermined in a terminal low frequency region of 10⁻² Hz in meltviscoelasticity determined by parallel plates. The gel ratio ispreferably 25 to 40% by weight, more preferably 25 to 35% by weight, andthe storage modulus is preferably 10⁴ to 10⁸ Pa, more preferably 10⁵ to10⁷ Pa. Below these ranges, the compression set and oil resistance ofthe thermoplastic elastomer composition obtained are bad. Above theseranges, softness is lost and moldability and processability are bad, andalso, tensile properties are deteriorated.

The thermoplastic elastomeric resin compositions, C-1 and C-2, are softand excellent in heat deformation resistance and moldability andprocessability, particularly in oil resistance, abrasion resistance andmechanical properties at a high temperature. Accordingly, they may beused for electrical wires, electric parts, industrial mechanical parts,medical apparatus, parts in the food fields, auto mobile parts andbuilding materials. The electrical wires and electric parts include, forexample, connectors, switch covers, plugs, gaskets, grommets, cablejacket curl cords?, electric wire insulation. The industrial mechanicalparts include, for example, pressure proof hoses, diaphragms, gaskets,packings, casters, grommets, roller coupling grips, hoses. The medicalapparatus and parts in food fields include syringe chips, medicinevessel closures, grommets, blood-gathering tube caps, cap seals. Theauto mobile parts include, for example, rack and pinion boots, shockabsorber dust boots, vacuum connectors, air ducts, tubes, run channels,grommets, handle covers, air bag outer cover steerings, mad guards,radiator hoses and brak hoses. The building materials include, forexample, window frame seals, expansion joints, sponge seals, handrailcoverings and non-slip materials for steps. Other applications includes,for example, grip materials such as pen grips, bicycle grips, toothbrash grips, parts for toys, mats, goggle, dust masks or gas masks andshoe bottoms.

The composition comprising components (a), (b), (c), and (d) may be meltbonded to various resins such as polyvinyl chloride, polysulfone,polyphenylene ether, ABS, polymethyl methacrylate, polycarbonate,polyolefin and polyamide.

EXAMPLES

The present invention is further elucidated with reference to thefollowing Examples and Comparison Examples, which is not intended tolimit the invention. The values in the Tables are represented in part byweight, unless otherwise indicated. The evaluation methods used were asfollows:

1) Hardness: determined in accordance with the Japanese IndustrialStandards (JIS) K 6301 and JIS S 6050 in Examples 1 to 10 and ComparisonExamples 1 to 12, and JIS K 7215 in Examples 11 to 23 and ComparisonExamples 13 to 66. Pressed sheets having a thickness of 6.3 mm were usedas test pieces.

2) Tensile strength: determined in accordance with JIS K 6301 using atest piece which was obtained by punching out a pressed sheet having athickness of 1 mm by a No. 3 dumbbell die. The tensile speed was 500mm/min. In Examples 1 to 10 and Comparison Examples 1 to 12, the testtemperature was room temperature. In Examples 11 to 23 and ComparisonExamples 13 to 66, the test temperature was room temperature, 120° C. or150° C.

3) Tensile elongation: determined in accordance with JIS K 6301 using atest piece which was obtained by punching out a pressed sheet having athickness of 1 mm by a No. 3 dumbbell die. The tensile speed was 500mm/min.

4) Stress at 100% elongation: determined in accordance with JIS K 6301using a test piece which was obtained by punching out a pressed sheethaving a thickness of 1 mm by a No. 3 dumbbell die. The tensile speedwas 500 mm 1 min.

5) Impact resilience: determined in accordance with BS903 using apressed sheet having a thickness of 4 mm as a test piece.

6) Compression set: determined in accordance with JIS K 6262 using apressed sheet having a thickness of 6.3 mm as a test piece. Conditions:25% deformation at 125° C.×72 hrs. or 150° C.×22 hrs. in Examples 1 to10 and Comparison Examples 1 to 12 and at 120° C.×72 hrs. in Examples 11to 23 and Comparison Examples 13 to 66.

7) Tearing strength: determined in accordance with JIS K 6301 using atest piece which was obtained by punching out a pressed sheet having athickness of 2.5 mm by a B type dumbbell die. The tensile speed was 500mm/min.

8) Oil resistance: determined in accordance with JIS K 6301 using a testpiece which was obtained by punching out a pressed sheet having athickness of 1 mm by a No. 3 dumbbell die. ASTM No. 2 oil was used. InExamples 1 to 10 and Comparison Examples 1 to 12, weight change wasmeasured after dipping at 120° C.×72 hrs. or after dipping at 30° C.×168hrs. In Examples 11 to 23 and Comparison Examples 13 to 66, weightchange and volume change were measured after dipping at 120° C.×70 hrs.

9) Stain resistance: determined in accordance with JIS K 6902 using apressed sheet having a thickness of 1 mm as a test piece. Test pieceswere stained by a shoe polish, left at 23° C. for 24 hrs. and washedwith water. Discoloration was observed visually.

10) Moldability in Examples 1 to 10 and Comparison Examples 1 to 12:determined by molding a composition into a sheet of 8.5×5×3 mm on an 80tons injection molding machine. When neither delamination nordeformation was observed and there was no flow mark which extremelydeteriorated appearance, moldability was evaluated as good.

11) Stickiness: evaluated as good when, on the molded sheet mentioned in(10) immediately above, neither bleeding nor blooming of low molecularweight substances was observed and no stickiness was felt in touch byfingers.

12) Taber abrasion: determined in accordance with JIS K 7204 using a 2mm thick pressed sheet. Weight loss by abrasion was determined after1,000 turns with a truck wheel, H-22.

13) Moldability in Examples 11 to 23 and Comparison Examples 13 to 66: acomposition was molded into a sheet of 12.5 mm×13.5 mm×1 mm by a 120tons injection molding machine in the following conditions:

molding temperature: 220° C.,

mold temperature: 40° C.,

injection speed: 55 mm/sec.,

injection pressure: 1400 kg/cm²,

holding pressure: 400 kg/cm²

injection time: 6 seconds,

cooling time: 45 seconds.

It was observed whether delamination, surface peeling, deformation orflow marks which extremely deteriorated appearance was present or not.

◯: good

Δ: slightly bad

×: bad

14) Bleed-out property: The molded sheet mentioned in (13) immediatelyabove, was compressed by 50% under the condition of 100° C.×22 hrs. Itwas observed whether bleeding or blooming of low molecular weightsubstances was visually observed or not, and whether stickiness was feltor not in tough by fingers.

◯: good

Δ: slightly bad

×: bad

15) Evaluation tests for adhesive property were carried out as follows:

The test method will be explained by reference to FIGS. 1 to 3. Thefollowing various resins were molded into sheet 3 of 150×25×4 mm on a120 tons injection molding machine in the following conditions:

molding machine: FS-120, ex Nissei Resin Industries Inc.,

molding temperature: 200° C. or 250° C., depending upon a recommendedtemperature for each resin,

mold temperature: 40 to 150° C.,

injection speed: 55 mm/sec.,

injection pressure: 1400 kg/cm²,

holding pressure: 400 kg/cm²,

injection time: 6 seconds,

cooling time: 45 seconds.

Resins Used:

Vinyl chloride, VDV030A, trade mark, ex Riken Vinyl Industries Inc.,

Polysulfone, Udel P-1700, trade mark, ex Teijin-Acomo Co.,

Modified polyphenylene ether, Xyron X9102, trade mark, ex Asahi KaseiIndustries Inc.,

ABS, JSR ABS38, trade mark, ex Japan Synthetic Rubber Co.,

Polystyrene, Styron G8073, trade mark, ex Asahi Kasei Industries Inc.,

Polymethyl methacrylate, Derpet SR8200, trade mark, ex Asahi KaseiIndustries Inc.,

Polycarbonate, Jupilon S-3000, trade mark, Mitsubishi Gas Chemical Co.,

High density polyethylene, 110J, trade mark, ex Idemitsu PetrochemicalCo.,

Polypropylene, RB110, trade mark, ex Tokuyama Co.,

Nylon, nylon-6, A1025, trade mark, ex Unitika Co.

A piece of paper, 4, of 75×25 mm was bonded to sheet 3 of the aforesaidresin as indicated in FIGS. 1 and 2 wherein the sizes are in millimeter.It was then inserted in a predetermined mold. Next, each resincomposition from the Examples and Comparison Examples was injectionmolded at a molding temperature of 220° C. (the other conditions weresame as mentioned above) to obtain bonded sheet 1, i.e., a test piecebefore bended, wherein sheet 2 of 3 mm thickness and sheet 3 of 4 mmthickness were welded on the surface A as indicated in FIGS. 1 and 2. Inthe Figures, sheet 2 is a sheet composed of each resin composition fromthe Examples and Comparison Examples. Sheet 2 was then bended at 180degrees in the direction indicated by arrow 5 to make test piece 7 asindicated in FIG. 3. Subsequently, the test piece was drawn at a tensilespeed of 50 mm/min. in the direction indicated by arrow 6 to determinethe adhesive strength using a load cell.

Materials Used:

Component (a): Hydrogenated Block Copolymer, Septon 4077, ex. KurarayCo.,

styrene content: 30% by weight,

isoprene content: 70% by weight,

number average molecular weight: 260,000,

weight average molecular weight: 320,000,

molecular weight distribution: 1.23, and

hydrogenation ratio: at least 90%.

Component (b): Non-Aromatic Softening Agent for Rubber, Diana ProcessOil,

PW-90, ex Idemitsu Kosan Co.,

type: paraffin type oil,

weight average molecular weight: 540,

content of aromatic components: not more than 0.1%,

paraffinic carbon content: 71%, and

naphthenic carbon content: 29%.

Component (c): Peroxide-Crosslinking Type Olefinic Resin

PE-1; BondFast BF-E, ex Sumitomo Chemical Co.,

type: epoxy group-containing ethylene copolymer

MFR: 3 g/10 min.

PE-2; BondFast 7L, ex Sumitomo Chemical Co.,

type: epoxy group-containing ethylene copolymer,

MFR: 3 g/10 min.

These were used in Examples 1 to 13 and Comparison Examples 1 to 12.

HE; ethylene-hexene copolymer, SP2520, trade mark, ex MitsuiPetrochemical Industries Inc.,

density: 0.928 g/cm3,

melt index, determined at 190° C. and a load of 2.16 kg: 1.7 g/10 min.,

used in Examples 11 to 23 and Comparison Examples 13 to 66.

Component (d): Peroxide-Decomposing Type Olefinic Resin

PP-1; CJ700, ex Mitsui Petrochemical Industries Inc.,

type: polypropylene (PP)

MFR: 7 g/10 min.,

crystallinity: Tm 166° C., ΔHm 82 J/mg,

used in the first step in Examples 1 to 5 and Comparison Examples 1 and2 and in Examples 11 to 23 and Comparison Examples 13 to 66.

PP-2; TPO E2640, ex Idemitsu Petrochemical Inc.,

type: low crystalline polypropylene

MFR: 2.5 g/10 min.,

used in the first step in Examples 6 to 10 and Comparison Examples 3 to12.

PP-3; BC03B, Mitsubishi Yuka Inc.,

type: polypropylene (PP)

MFR: 30 g/10 min.,

used in the third step in Examples 1 to 10 and Comparison Examples 1 to7 and 9 to 12.

Component (e): Polyester Type Elastomer, Polyamide Type Elastomer orPolyurethane Type Elastomer

TPEE-1; 4047, ex Toray-Du Pont Inc.,

type: polyester type elastomer

TPAE-1; 2533SA01, ex ATOCHEM Inc.,

type: polyamide type elastomer

TPUE-1: E190, Nippon Mirakutoran Inc.,

type: polyurethane type elastomer

Component (f): Hydrogenated Petroleum Resin,

Imarv P-140, ex Idemitsu Petrochemical Inc.,

type: hydrogenated petroleum resin, C5-aromatic type copolymerichydrogenated resin

Component (g): Inorganic Filler

RS400, ex Sankyo Seihun Co.,

type: calcium carbonate

Component (h): Organic Peroxide

Perkadox 14, ex Kayaku Akzo Co.,

type: 1,3-bis(t-butylperoxyisopropyl)benzene

used in Examples 1 to 10 and Comparison Examples 1 to 12.

KayahexaAD, trade mark, ex Kayaku Akzo Co.,

used in Examples 11 to 23 and Comparison Examples 13 to 66.

Component (i): Crosslinking Aid

NK ester 3G, ex Shin-Nakamura Chemical Co.,

type: triethylene glycol dimethacrylate

Daiso DAP Monomer, ex Daiso Co.

type: diallyl phthalate monomer

Component (j): Antioxidant

PEP-36, ex Asahi Denka Co., and

Ir-1010, ex Ciba-Geigy,

used in Examples 1 to 10 and Comparison Examples 1 to 12.

Irganox B220, trade mark, ex Nippon Ciba-Geigy, used in Examples 11 to23 and Comparison Examples 13 to 66.

Component (k): Liquid Polybutadiene

R45HT, trade mark, ex Idemitsu Petrochemical Industries Inc., havinghydroxyl groups (acryl type, primary) and copolymerization-reactiveunsaturated double bonds (1,4 bonds: 80%). The number average molecularweight: 2,800

Component (l): Unsaturated Glycidyl Compound

glycidyl methacrylate, ex Kanto Kagaku Co.

Component (m): Unsaturated Carboxylic Acid Derivative

maleic anhydride, ex Kanto Kagaku Co.

Component (n):

thermoplastic polyester type elastomer (TPEE), Nouvelan R4410ZN, trademark, ex Teijin Co.,

thermoplastic polyamide type elastomer (TPAE), Pebax 2533SA01, trademark, ex Toray Co.,

thermoplastic polyurethane type elastomer (TPUE), Pandex T-1180N, trademark, ex Dai-Nippon Ink Chemical Industries Inc.,

polymethylpentene (TPX), RT-31, trade mark, ex Mitsui PetrochemicalIndustries Inc.,

nylon-6, A-1025, trade mark, ex Unitika Co.

Examples 1 to 10 and Comparison Examples 1 to 12, for Process P-1 andComposition C-1

Preparation Process;

In a first step, components (a) to (c), a part of component (d),components (e) and (f), an inorganic filler and an anti-oxidant werekneaded. In a second step, an organic peroxide and a crosslinking aidwere kneaded with the aforesaid kneaded product. In a third step, thekneaded product and the remaining part of component (d) were kneaded.

In each of the first, second and third steps, a twin-screw kneader wasoperated at the following temperature at a screw rotation of 100 rpm:

first step; 230 to 240° C.,

second step; 180 to 220° C., and

third step; 200 to 220° C.

Example 1

The components were used in the amounts represented in Table 1 toprepare a resin composition. The results are as shown in Table 1. Thecomposition of the invention was excellent in mechanical properties, oilresistance, stain resistance and stickiness.

Comparison Examples 1 and 2

In Comparison Example 1, no use was made of component (e), i.e.polyester type polymer, polyamide type polymer, or polyurethane typepolymer, which are the components of the present invention. InComparison Example 2, component (e) was used in an amount exceeding therange of the present invention. The results are as shown in Table 1. InComparison Example 1, in which component (e) was not used, the oilresistance and stain resistance were poor. In Comparison Example 2, inwhich the amount of component (e) exceeded the range of the presentinvention, the product was hard and, therefore, moldability was poor.

Examples 2 and 3

In these Examples, the amount of component (e) was different from thatin Example 1. The amount of each component and the results are as shownin Table 2. Good results were obtained as in Example 1.

Examples 4 and 5

In these Examples, another types of the resins were further blended in acomposition as component (c) in addition to the resin used in Example 1.Use were made of a polyamide type copolymer in Example 4 and apolyurethane type copolymer in Example 5 as component (e). The amount ofeach component and the results are as shown in Table 2. Good resultswere obtained as in Example 1.

Example 6

In this Example, use was made of component (f), hydrogenated petroleumresin, which was an optional component in the present invention. Theamount of each component and the results are as shown in Table 3. Thecomposition was excellent in mechanical properties, oil resistance,stain resistance and stickiness.

Comparison Example 3

In this Comparison Example, the amount of component (f), which was thecomponent according to the invention, exceeded the range of the presentinvention. The amount of each component and the results are as shown inTable 3. Mechanical properties, oil resistance and stain resistance werepoor and the molded article exhibited surface tackiness.

Examples 7 and 8

In these Examples, the amount of component (f), hydrogenated petroleumresin, was different from that in Example 6. The amount of eachcomponent and the results are as shown in Table 3. Good results wereobtained as in Example 6.

Comparison Examples 4 and 5

In Comparison Example 4, no use was made of component (c), i.e. aperoxide crosslinking type olefinic resin, which was the componentaccording to the present invention. In Comparison Example 5, component(c) was used in the amount exceeding the range of the present invention.The amount of each component and the results are as shown in Table 4. InComparison Example 4, the tensile elongation, oil resistance and stainresistance were poor. In Comparison Example 5, the compression set, oilresistance and stain resistance were poor.

Comparison Examples 6 and 7

The amount of component (b), i.e. a non-aromatic type softening agentfor rubber, was below the range of the present invention in ComparisonExample 6, while it was above the range in Comparison Example 7. Theamount of each component and the results are as shown in Table 4. InComparison Example 6, neither press molding nor injection molding couldbe carried out because of the occurrence of abnormal torque and abnormalresin pressure during the preparation. In Comparison Example 7, themechanical properties, oil resistance and stain resistance were poor andthe molded article exhibited stickiness.

Comparison Examples 8 and 9

The amount of component (d), i.e. a peroxide decomposing type olefinicresin, was below the range of the present invention in ComparisonExample 8, while it was above the range in Comparison Example 9. Inaddition, component (d) was not blended in the composition in the thirdstep in Comparison Example 8. The amount of each component and theresults are as shown in Table 5. In Comparison Example 8, neither pressmolding nor injection molding could be carried out because of theoccurrence of abnormal torque and abnormal resin pressure during thepreparation. In Comparison Example 9, the resin composition was hardand, therefore, rubber elasticity was lost.

Comparison Example 10

In this Comparison Example, the amount of component (g), i.e. inorganicfiller, which was an optional component in the present invention, wasabove the range of the present invention. The amount of each componentand the results are as shown in Table 5. The mechanical properties, oilresistance and stain resistance were poor.

Examples 9 and 10

The amounts of the organic peroxide and the crosslinking aid which wereblended in the second step were different from those in Example 7. Theamount of each component and the results are as shown in Table 6. Goodresults were obtained as in Example 7.

Comparison Examples 11 and 12

In Comparison Example 11, the organic peroxide and the crosslinking aidwere not used, while very large amounts of them were used in ComparisonExample 12. The amount of each component and the results are as shown inTable 6. In Comparison Example 11, the rubber elasticity deterioratedand the oil resistance and stain resistance were poor. The moldedarticle obtained exhibited stickiness. In Comparison Example 12, neitherpress molding nor injection molding could be carried out because of theoccurrence of abnormal torque and abnormal resin pressure during thepreparation.

TABLE 1 Comp. Comp. Ex. 1 Ex. 1 Ex. 2 (a) SEPS 4077 100 100 100 (b)Process oil PW90 120 120 120 (c) PE-1 BF-E 23.6 23.6 23.6 PE-2 7L (d)PP-1 CJ700 20 20 20 PP-2 E2640 PP-3 BC03B 20 20 20 (e) TPEE-1 4047 160 01300 TPAE-1 2533SA01 TPUE-1 E190 (f) Petroleum resin P-140 (g) FillerRS400 20 20 20 Organic peroxide Perkadox 14 2.3 2.3 2.3 Crosslinking aidNK Ester 3G 4.1 4.1 4.1 Daiso DAP Monomer 0.9 0.9 0.9 Antioxidant PEP360.2 0.2 0.2 Ir1010 0.2 0.2 0.2 Hardness after HDA 15 seconds 74 45 95Tensile strength MPa 6.3 7 18.6 100% Modulus MPa 4.7 1.5 6.4 Elongation% 250 550 520 Impact resilience % 45 61 58 Compression set 120° C. × 72hrs (%) 54 43 72 150° C. × 22 hrs (%) 61 58 78 Tearing strength kN/m 4918 78 Oil resistance ASTM No. 2 18 68 10 (120° C. × 72 hrs) (%) PW90 2.818 0.5 (30° C. × 168 hrs) Stain resistance ◯ X ◯ Moldability ◯ ◯ ΔStickiness ◯ ◯ ◯

TABLE 2 Ex. 2 Ex. 3 Ex. 4 Ex. 5 (a) SEPS 4077 100 100 100 100 (b)Process oil PW90 120 120 120 120 (c) PE-1 BF-E 23.6 23.6 3.6 3.6 PE-2 7L20 20 (d) PP-1 CJ700 20 20 20 20 PP-2 E2640 PP-3 BC03B 20 20 20 20 (e)TPEE-1 4047 250 400 TPAE-1 2533SA01 250 TPUE-1 E190 250 (f) Petroleumresin P-140 (g) Filler RS400 20 20 20 20 Organic peroxide Perkadox 142.3 2.3 2.3 2.3 Crosslinking aid NK Ester 3G 4.1 4.1 4.1 4.1 Daiso DAPMonomer 0.9 0.9 0.9 0.9 Antioxidant PEP36 0.2 0.2 0.2 0.2 Ir1010 0.2 0.20.2 0.2 Hardness after HDA 15 seconds 76 81 78 72 Tensile strength MPa6.1 5.4 5.1 5.4 100% Modulus MPa 4.8 4.8 4.1 4.2 Elongation % 220 150260 280 Impact resilience % 43 42 38 45 Compression set 120° C. × 72 hrs(%) 58 60 67 60 150° C. × 22 hrs (%) 64 65 78 68 Tearing strength kN/m55 68 52 46 Oil resistance ASTM No. 2 16 12 14 16 (120° C. × 72 hrs) (%)PW90 2.2 1.8 1.9 2.3 (30° C. × 168 hrs) Stain resistance ◯ ◯ ◯ ◯Moldability ◯ ◯ ◯ ◯ Stickiness ◯ ◯ ◯ ◯

TABLE 3 Comp. Ex. 6 Ex. 7 Ex. 8 Ex. 3 (a) SEPS 4077 100 100 100 100 (b)Process oil PW90 180 180 180 180 (c) PE-1 BF-E 23.6 43.6 63.6 43.6 PE-27L (d) PP-1 CJ700 PP-2 E2640 10 10 10 10 PP-3 BC03B 20 20 20 20 (e)TPEE-1 4047 250 250 250 250 TPAE-1 2533SA01 TPUE-1 E190 (f) Petroleumresin P-140 10 10 10 150 (g) Filler RS400 20 20 20 20 Organic peroxidePerkadox 14 2.3 2.3 2.3 2.3 Crosslinking aid NK Ester 3G 4.1 4.1 4.1 4.1Daiso DAP 0.9 0.9 0.9 0.9 Monomer Antioxidant PEP36 0.2 0.2 0.2 0.2Ir1010 0.2 0.2 0.2 0.2 Hardness after HDA 15 64 66 69 56 seconds Tensilestrength MPa 5.3 5.5 5.8 4.8 100% Modulus MPa 4.6 4.7 4.6 3.5 Elongation% 280 300 310 240 Impact resilience % 48 47 46 45 Compression set 120°C. × 72 hrs 54 58 60 65 (%) 150° C. × 22 hrs 62 65 68 75 (%) Tearingstrength kN/m 48 46 46 40 Oil resistance ASTM No. 2 28 25 25 58 (120° C.× 72 hrs) (%) PW90 4.5 4.3 4.1 10 (30° C. × 168 hrs) Stain resistance ◯◯ ◯ Δ Moldability ◯ ◯ ◯ X Stickiness ◯ ◯ ◯ X

TABLE 4 Comp. Ex. 4 Comp. Ex. 5 Comp. Ex. 6 Comp. Ex. 7 (a) SEPS 4077100 100 100 100 (b) Process oil PW90 180 180 15 350 (c) PE-1 BF-E 0 18043.6 43.6 PE-2 7L (d) PP-1 CJ700 PP-2 E2640 10 10 10 10 PP-3 BC03B 20 2020 20 (e) TPEE-1 4047 250 250 250 250 TPAE-1 2533SA01 TPUE-1 E190 (f)Petroleum resin P-140 10 10 10 10 (g) Filler RS400 20 20 20 20 Organicperoxide Perkadox 14 2.3 2.3 2.3 2.3 Crosslinking aid NK Ester 3G 4.14.1 4.1 4.1 Daiso DAP Monomer 0.9 0.9 0.9 0.9 Antioxidant PEP36 0.2 0.20.2 0.2 Ir1010 0.2 0.2 0.2 0.2 Hardness after HDA 15 seconds 60 75unproductable 48 Tensile strength MPa 8.2 10.3 3.2 100% Modulus MPa 2.15.1 1.6 Elongation % 120 450 180 Impact resilience % 44 45 43Compression set 120° C. × 72 hrs (%) 60 65 73 150° C. × 22 hrs (%) 65 7480 Tearing strength kN/m 30 50 38 Oil resistance ASTM No. 2 40 45 52(120° C. × 72 hrs) (%) PW90 5.5 5 12 (30° C. × 168 hrs) Stain resistanceΔ Δ Δ Moldability ◯ ◯ X Stickiness ◯ ◯ X

TABLE 5 Comp. Comp. Comp. Ex. 8 Ex. 9 Ex. 10 (a) SEPS 4077 100 100 100(b) Process oil PW90 180 180 180 (c) PE-1 BF-E 43.6 43.6 43.6 PE-2 7L(d) PP-1 CJ700 PP-2 E2640 5 10 10 PP-3 BC03B 0 180 20 (e) TPEE-1 4047250 250 250 TPAE-1 2533SA01 TPUE-1 E190 (f) Petroleum resin P-140 10 1010 (g) Filler RS400 20 20 120 Organic peroxide Perkadox 14 2.3 2.3 2.3Crosslinking aid NK Ester 3G 4.1 4.1 4.1 Daiso DAP Monomer 0.9 0.9 0.9Antioxidant PEP36 0.2 0.2 0.2 Ir1010 0.2 0.2 0.2 Hardness after HDA 15seconds un- 98 75 product- able Tensile strength MPa 17.2 5 100% ModulusMPa 5.6 4.3 Elongation % 550 80 Impact resilience % 32 30 Compressionset 120° C. × 72 hrs (%) 78 65 150° C. × 22 hrs (%) 92 73 Tearingstrength kN/m 52 37 Oil resistance ASTM No. 2 18 20 (120° C. × 72 hrs)(%) PW90 1.8 3.5 (30° C. × 168 hrs) Stain resistance ◯ X Moldability ◯ XStickiness ◯ ◯

TABLE 6 Ex. 9 Ex. 10 Comp. Ex. 11 Comp. Ex. 12 (a) SEPS 4077 100 100 100100 (b) Process oil PW90 180 180 180 180 (c) PE-1 BF-E 43.6 43.6 43.643.6 PE-2 7L (d) PP-1 CJ700 PP-2 E2640 10 10 10 10 PP-3 BC03B 20 20 2020 (e) TPEE-1 4047 250 250 250 250 TPAE-1 2533SA01 TPUE-1 E190 (f)Petroleum resin P-140 10 10 10 10 (g) Filler RS400 20 20 20 20 Organicperoxide Perkadox 14 3 3.75 0 20 Crosslinking aid NK Ester 3G 5.4 6.75 036 Daiso DAP Monomer 1.2 1.5 0 8 Antioxidant PEP36 0.2 0.2 0.2 0.2Ir1010 0.2 0.2 0.2 0.2 Hardness after HDA 15 seconds 67 69 70unproductable Tensile strength MPa 5.1 4.8 7 100% Modulus MPa 4.8 5 3.2Elongation % 260 210 580 Impact resilience % 48 50 53 Compression set120° C. × 72 hrs (%) 52 55 80 150° C. × 22 hrs (%) 60 62 95 Tearingstrength kN/m 52 50 33 Oil resistance ASTM No. 2 20 18 65 (120° C. × 72hrs) (%) PW90 4 3.5 20 (30° C. × 168 hrs) Stain resistance ◯ ◯ XMoldability ◯ ◯ ◯ Stickiness ◯ ◯ X

The following Examples and Comparison Examples are for the processes P-2and P-3 and the Cmposition C-2.

Examples 11 and 12 and Comparison Examples 13 to 22

Component (n) was not used here.

Each component was used in the amount indicated in Table 7 in part byweight. The whole amounts of components (a), (b), (c), (k), (l), (m),(g) and (j) and a part of component (d), which amount is indicatedbefore symbol “+” in Table 7, were introduced all together into a twinextruder with an L/D of 62.5 and started to be melt kneaded at akneading temperature of 180° C. and a screw rotation speed of 350 rpm.Next, the whole amounts of components (h) and (i) were side fed and themelt kneading was still continued. Subsequently, the remaining part ofcomponent (d), which amount is indicated after symbol “+” in Table 7,was side fed, melt kneaded at 200° C. and pelletized. In ComparisonExample 13, the whole of component (d) was introduced into thetwin-screw extruder together with the whole of components (a), (b), (c),(k), (l), (m), (g) and (j) and melt kneaded. The pellets obtained wereput in a predetermined mold and then pressed in the conditions of 220°C. and 50 kg/cm² to obtain each sheet for the aforesaid evaluationmethods (1) to (4), (6) to (8) and (12). For evaluation methods (13) and(14), the pellets thus obtained were injection molded in the conditionsdescribed in evaluation method (13). For evaluation method (15), thepellets thus obtained were injection molded in the conditions describedin evaluation method (15).

The results are as shown in Table 8.

TABLE 7 Amount of Component, Ex. Comparison Example part by weight 11 1213*¹ 14 15 16 17 18 19 20 21 22 (a) 100 100 100 100 100 100 100 100 100100 100 100 (b) 100 100 100 100 100 100 100 100 100 100 100 100 (c) 5 05 5 5 5 5 5 5 5 5 5 (d) 15 + 30 15 + 30 45 15 + 30 15 + 30 15 + 30 15 +30 15 + 30 15 + 30 15 + 30 15 + 30 15 + 30 (k) 10 10 10 0 0 40 10 10 1010 10 10 (l) 4 4 4 0 4 4 0 20 4 4 4 4 (m) 4 4 4 0 4 4 4 4 0 20 4 4 (n) —— — — — — — — — — — — (g) 20 20 20 20 20 20 20 20 20 20 20 20 (h) 1.751.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 4.5 0 (i) 3.15 3.15 3.153.15 3.15 3.15 3.15 3.15 3.15 3.15 10 0 (j) 0.4 0.4 0.4 0.4 0.4 0.4 0.40.4 0.4 0.4 0.4 0.4 *¹Component (d) was kneaded all in step (I).

TABLE 8 Ex. Comparison Example Properties of the composition 11 12 13*¹14 15 16 17 18 19 20 21 22 Specific gravity 0.92 0.92 0.92 0.92 0.920.93 0.92 0.92 0.92 0.92 — 0.92 Hardness, 65 65 62 68 66 64 65 63 65 62— 52 after HDA 15 seconds Tensile strength, MPa 23° C. 11.5 11.5 6 9.59.7 9 10 9.5 10 9.8 — 13 120° C. 0.3 0.3 0.3 0 0 0 0 0 0 0 — 0 150° C. 00 0 0 0 0 0 0 0 0 — 0 Tensile elongation, % 850 850 450 650 750 780 800700 800 680 — 900 Stress at 100% elongation, MPa 5.3 5.3 3.8 4.3 3.8 3.53.8 4 3.8 3.3 — 3 Tearing strength, kN/m 58 58 65 50 48 45 45 40 45 38 —40 Compression set, % 40 40 40 48 48 58 48 60 50 62 — 68 Taber abrasion,mg 200 200 200 250 250 250 250 300 250 300 — 350 Oil resistance Weightchange, % 60 60 60 65 — — — — — — — soluble Volume change, % 50 50 50 53— — — — — — — — Moldability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ *² ◯ Bleedout property ◯◯ ◯ ◯ ◯ ◯ ◯ Δ ◯ Δ — ◯ *¹Component (d) was kneaded all in step (I). *²Notest piece could be produced

In Examples 11 and 12, the elastomer compositions were preparedaccording to the present process. Both elastomer compositions exhibitgood properties whether the optional component (c) was used or not.

Meanwhile, in Comparison Example 13, component (d) was kneaded all instep (i) with the other components in the same composition as in Example11. Considerable decreases in tensile strength, tensile elongation andelongation stress were observed. In Comparison Example 14, components(k), (l) and (m) were not blended. Decreases in tensile strength,tensile elongation, elongation stress and tearing strength wereobserved. The taber abrasion increased. In addition, the oil resistancedeteriorated slightly. In Comparison Example 15, component (k) was notblended, while in Comparison Example 16, the amount of component (k) wasabove the range of the present invention. In both compositions,decreases in tensile strength, tensile elongation, elongation stress andtearing strength were observed and the taber abrasion increased. InComparison Example 17, component (l) was not blended, while inComparison Example 18, the amount of component (l) was above the rangeof the present invention. In both compositions, decreases in tensilestrength, tensile elongation, elongation stress and tearing strengthwere observed and the taber abrasion increased. In Comparison Example18, the increase in taber abrasion was remarkable and the bleedoutproperty deteriorated slightly. In Comparison Example 19, component (m)was not blended, while in Comparison Example 20, the amount of component(m) was above the range of the present invention. In both compositions,decreases in tensile strength, tensile elongation, elongation stress andtearing strength were observed and the taber abrasion increased. InComparison Example 20, the incerease in taber abrasion was remarkableand the bleedout property deteriorated slightly. In Comparison Example21, the amount of component (h) was above the range of the presentinvention. Overload took place on the twin-screw extruder and strandappearance deteriorated remakably. Accordingly, the preparation of thepellets could not be carried out and, therefore, no test piece could beprepared. As a result, any characteristic property could not bedetermined. In Comparison Example 22, component (h) was not blended.Decreases in hardness, elongation stress and tearing strength wereobserved and the taber abrasion increased. In the oil resistance test,the composition was completely dissolved in ASTM No. 2 oil. Accordingly,it was not recognized to have oil resistance at all.

Examples 13 to 15 and Comparison Examples 23 to 36

A thermoplastic polyester type elastomer (TPEE) was used as component(n).

Each component was used in the amount indicated in Tables 9 and 11 inpart by weight. The whole amounts of components (a), (b), (c), (d), (k),(l), (m), (g) and (j) were introduced all together into a twin-screwextruder with a L/D of 62.5 and started to be melt kneaded at a kneadingtemperature of 180 to 210° C. and a screw rotation speed of 350 rpm.Next, the whole amounts of components (h) and (i) were side fed and themelt kneading was still continued. Subsequently, the whole of component(n), TPEE, was side fed, melt kneaded at 200 to 220° C. and pelletized.In Comparison Example 23, the whole of component (n) was introduced intothe twin-screw extruder, together with the whole of components (a), (b),(c), (d), (k), (l), (m), (g) and (1), and melt kneaded at 180 to 220° C.Characteristics were determined as mentioned above.

The results are as shown in Tables 10 and 12.

TABLE 9 Amount of Component, Example part by weight 13 14 15 (a) 100 100100 (b) 100 100 100 (c) 5 5 0 (d) 15 15 15 (k) 10 10 10 (l) 4 4 4 (m) 44 4 (n) TPEE 400 750 400 (g) 20 20 20 (h) 1.75 1.75 1.75 (i) 3.15 3.153.15 (j) 0.4 0.4 0.4

TABLE 10 Example Properties of the composition 13 14 15 Specific gravity1.03 1.14 1.03 Hardness, after HDA 15 seconds 74 82 74 Tensile strength,MPa 23° C. 19.6 23.5 19.6 120° C. — — — 150° C. — — — Tensileelongation, % 840 860 840 Stress at 100% elongation — — — Tearingstrength, kN/m 58 75 58 Compression set, % 55 — — Taber abrasion, mg 50— — Oil resistance Weight change, % — — — Volume change, % — — —Moldability ◯ ◯ ◯ Bleedout property ◯ ◯ ◯ Adhesive property, kg/25 mmvinyl chloride 8 12 8 polysulfone 7 10 7 polyphenylene ether 1 3 1 ABS 810 8 polystyrene 2 1.5 2 polymethyl methacrylate 4 4.5 4 polycarbonate12 14 12 high-density polyethylene 0.5 0 0.5 polypropylene 0.5 0 0.5nylon 0 0 0

TABLE 11 Amount of Component, Comparison Example part by weight 23*³ 2425 26 27 28 29 30 31 32 33 34 35 36 (a) 100 100 100 100 100 100 100 100100 100 100 100 100 100 (b) 100 100 100 100 100 100 100 100 10 350 100100 100 100 (c) 5 5 5 5 5 5 5 5 5 5 120 5 5 5 (d) 15 15 15 15 15 15 1515 15 15 15 2 120 15 (k) 10 0 40 10 10 10 10 10 10 10 10 10 10 10 (l) 44 4 0 20 4 4 4 4 4 4 4 4 4 (m) 4 4 4 4 4 0 20 4 4 4 4 4 4 4 (n) TPEE 400400 400 400 400 400 400 400 400 400 400 400 400 8 (g) 20 20 20 20 20 2020 20 20 20 20 20 20 20 (h) 1.75 1.75 1.75 1.75 1.75 1.75 1.75 0 1.751.75 1.75 1.75 1.75 1.75 (i) 3.15 3.15 3.15 3.15 3.15 3.15 3.15 0 3.153.15 3.15 3.15 3.15 3.15 (j) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.40.4 0.4 0.4 *³Comparison Example in which component (n), TPEE, waskneaded all in step (I).

TABLE 12 Comparison Example Properties of the composition 23*³ 24 25 2627 28 29 30 31 32 33 34 35 36 Specific gravity 1.03 1.03 1.02 1.03 —1.03 1.03 1.03 — — — — — 0.93 Hardness, after HDA 15 seconds 65 73 74 74— 73 75 73 — — 97 — 97 45 Tensile strength, MPa 23° C. 5.3 18.4 19.0 13— 19.4 16.5 14.8 — 9.8 — — — 5.8 120° C. 0 — — — — — — — — — — — — —150° C. 0 — — — — — — — — — — — — — Tensile elongation, % 350 850 800600 — 850 720 680 — 470 — — — 520 Stress at 100% elongation, MPa — — — —— — — — — — — — — — Tearing strength, kN/m 40 60 57 66 65 56 58 — — — —— — 48 Compression set, % 55 — — — — — — — — — — — — — Taber abrasion,mg 300 — — — — — — — — — — — — — Oil resistance Weight change, % — — — —— — — — — — — — — — Volume change, % — — — — — — — — — — — — — —Moldability ◯ Δ ◯ Δ ◯ Δ ◯ ◯ X ◯ ◯ X ◯ Δ Bleedout property ◯ ◯ Δ ◯ Δ ◯ Δ◯ ◯ X X ◯ X ◯ Adhesive property, kg/25 mm vinyl chloride 3 — — — — — — —— — — — — 0 polysulfone 3 — — — — — — — — — — — — 0 polyphenylene ether0.5 — — — — — — — — — — — — 0 ABS 3.5 — — — — — — — — — — — — 0.5polystyrene 1 — — — — — — — — — — — — 0.5 polymethyl methacrylate 2 — —— — — — — — — — — — 0 polycarbonate 35 — — — — — — — — — — — — 0high-density polyethylene 0.5 — — — — — — — — — — — — 1.5 polypropylene0.5 — — — — — — — — — — — — 3 nylon 0 — — — — — — — — — — — — 0*³Comparison Example in which component (n), TPEE, was kneaded all instep (I).

In Examples 13 to 15, the elastomer compositions were prepared accordingto the present process. In Example 14, the amount of (n) blendedincreased within the range of the present invention. The hardness,tensile strength, tensile elongation and tearing strength increased. Theadhesive property to polystyrene, high density polyethylene andpolypropylene decreased, while that to the other resins increased. InExample 15, optional component (c) was not blended. The properties weregood as in Example 13.

Meanwhile, in Comparison Example 23, component (n) was kneaded all instep (I) with the other components in the same compositions as inExample 13. Decreases in hardness, tensile strength, tensile elongationand tearing strength were observed and the taber abrasion increased. Theadhesive property to all of the resins except polycarbonate, highdensity polyethylene and polypropylene decreased. In Comparison Example24, component (k) was not blended, while in Comparison Example 25, theamount of component (k) was above the range of the present invention. InComparison Example 24, the tensile strength decreased and themoldability deteriorated slightly. In Comparison Example 25, decreasesin tensile strength, tensile elongation and tearing strength wereobserved and the bleedout property deteriorated slightly. In ComparisonExample 26, component (l) was not blended, while in Comparison Example27, the amount of component (l) was above the range of the presentinvention. In Comparison Example 26, the tensile strength and tensileelongation decreased and the moldability deteriorated slightly. InComparison Example 27, the bleedout property deteriorated slightly. InComparison Example 28, component (m) was not blended, while inComparison Example 29, the amount of component (m) was above the rangeof the present invention. In Comparison Example 28, the moldabilitydeteriorated slightly. In Comparison Example 29, the tensile strengthand tensile elongation decreased and the bleedout property deterioratedslightly. In Comparison Example 30, organic peroxide (h) was notblended. The tensile strength and tensile elongation decreasedconsiderably. In Comparison Example 31, the amount of component (b) wasbelow the range of the present invention, while in Comparison Example32, it was above the range. In Comparison Example 31, the moldabilitydeteriorated considerably. In Comparison Example 32, the tensilestrength and tensile elongation decreased considerablly and the bleedoutproperty deteriorated considerably. In Comparison Example 33, the amountof component (c) was above the range of the present invention. Thehardness was too high and the bleedout property deterioratedconsiderably. In Comparison Example 34, the amount of component (d) wasbelow the range of the present invention, while in Comparison Example35, it was above the range. In Comparison Example 34, the moldabilitydeteriorated considerably. In Comparison Example 35, the hardness wastoo high and the bleedout property deteriorated considerably. InComparison Example 36, the amount of component (n) was below the rangeof the present invention. Decreases in hardness, tensile strength,tensile elongation and tearing strength were observed and themoldability deteriorated slightly. The adhesive property decreased inall of the resins except high density polyethylene and polypropylene.

Example 16 and Comparison Examples 37 to 44

A thermoplastic polyurethane type elastomer (TPUE) was used as component(n).

Each component was used in the amount indicated in Table 13 in part byweight. Pelletization was carried out as in the case where athermoplastic polyester type elastomer (TPEE) was used as component (n),after which the properties of the composition were determined.

The results are as shown in Table 14.

TABLE 13 Amount of Component, Ex. Comparison Example part by weight 1637*³ 38 39 40 41 42 43 44 (a) 100 100 100 100 100 100 100 100 100 (b)100 100 100 100 100 100 100 100 100 (c) 5 5 5 5 5 5 5 5 5 (d) 15 15 1515 15 15 15 15 15 (k) 10 10 0 40 10 10 10 10 10 (l) 4 4 4 4 0 20 4 4 4(m) 4 4 4 4 4 4 0 20 4 (n) TPUE 400 400 400 400 400 400 400 400 400 (g)20 20 20 20 20 20 20 20 20 (h) 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 0(i) 3.15 3.15 3.15 3.15 3.15 3.15 3.15 3.15 0 (j) 0.4 0.4 0.4 0.4 0.40.4 0.4 0.4 0.4 *³Comparison Example in which component (n), TPUE, waskneaded all in step (I).

TABLE 14 Ex. Comparison Example Properties of the composition 16 37*³ 3839 40 41 42 43 44 Specific gravity 1.07 1.07 1.07 1.07 1.07 1.07 1.071.07 1.07 Hardness, after HDA 15 seconds 67 67 68 69 67 66 67 69 69Tensile strength, MPa 23° C. 18.2 18.2 17.7 16.6 17.9 15.7 12.1 18.416.9 120° C. — — — — — — — — — 150° C. — — — — — — — — — Tensileelongation, % 570 570 540 600 540 480 620 620 640 Stress at 100%elongation, MPa — — — — — — — — — Tearing strength, kN/m 55 38 — — — — —— — Compression set, % 54 80 — — — — — — — Taber abrasion, mg 20 250 — —— — — — — Oil resistance Weight change, % — — — — — — — — — Volumechange, % — — — — — — — — — Moldability ◯ ◯ Δ ◯ Δ ◯ Δ ◯ ◯ Bleedoutproperty ◯ ◯ ◯ Δ ◯ Δ ◯ Δ ◯ Adhesive property, kg/25 mm vinyl chloride 73 — — — — — — — polysulfone 6 2 — — — — — — — polyphenylene ether 1 0.5— — — — — — — ABS 8 3 — — — — — — — polystyrene 2 1 — — — — — — —polymethyl methacrylate 4 2 — — — — — — — polycarbonate 12 4 — — — — — —— high-density polyethylene 0.5 0 — — — — — — — polypropylene 0.5 0 — —— — — — — nylon 0 0 — — — — — — — *³Comparison Example in whichcomponent (n), TPUE, was kneaded all in step (I).

In Example 16, the elastomer composition was prepared according to thepresent process. The properties were good.

Meanwhile, in Comparison Example 37, component (n) was kneaded all instep (I) with the other components in the same composition as in Example16. The tearing strength decreased and the taber abrasion increasedconsiderably. The adhesive property decreased for all of the resins. InComparison Example 38, component (k) was not blended, while inComparison Example 39, the amount of component (k) was above the rangeof the present invention. In both compositions, the tensil strengthdecreased. In Comparison Example 38, the moldability deterioratedslightly, while in Comparison Example 39, the bleedout propertydeteriorated slightly. In Comparison Example 40, component (l) was notblended, while in Comparison Example 41, the amount of component (l) wasabove the range of the present invention. In Comparison Example 40, thetensile strength and tensile elongation decreased slightly and themoldability deteriorated slightly. In Comparison Example 41, the tensilestrength and tensile elongation decreased and the bleedout propertydeteriorated slightly. In Comparison Example 42, component (m) was notblended, while in Comparison Example 43, the amount of component (m) wasabove the range of the present invention. In Comparison Example 42, thetensile strength decreased considerably and the moldability deterioratedslightly. In Comparison Example 43, the bleedout property deterioratedslightly. In Comparison Example 44, organic peroxide (h) was notblended. The tensile strength decreased considerably.

Example 17 and Comparison Examples 45 to 53

A thermoplastic polyamide type elastomer (TPAE) was used as component(n).

Each component was used in the amount indicated in Table 15 in part byweight. Pelletization was carried out as in the case where athermoplastic polyester type elastomer (TPEE) was used as component (n),after which the properties of the composition were determined. Theresults are as shown in Table 16.

TABLE 15 Amount of Component, Ex. Comparison Example part by weight 1745*³ 46 47 48 49 50 51 52 53 (a) 100 100 100 100 100 100 100 100 100 100(b) 100 100 100 100 100 100 100 100 100 100 (c) 5 5 5 5 5 5 5 5 5 5 (d)15 15 15 15 15 15 15 15 15 15 (k) 10 10 0 10 0 40 10 10 10 10 (l) 4 4 04 4 4 0 20 4 4 (m) 4 4 0 4 4 4 4 4 0 20 (n) TPAE 400 400 400 400 400 400400 400 400 400 (g) 20 20 20 20 20 20 20 20 20 20 (h) 1.75 1.75 1.75 01.75 1.75 1.75 1.75 1.75 1.75 (i) 3.15 3.15 3.15 0 3.15 3.15 3.15 3.153.15 3.15 (j) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 *³ComparisonExample in which component (n), TPAE, was kneaded all in step (I).

TABLE 16 Ex. Comparison Example Properties of the composition 17 45*³ 4647 48 49 50 51 52 53 Specific gravity 0.98 0.98 0.98 0.98 0.98 0.98 0.980.98 0.98 0.98 Hardness, after HDA 15 seconds 70 68 75 65 70 71 70 70 7070 Tensile strength, MPa 23° C. 15.5 10 5.2 4.8 10.5 13 13.5 11.5 10 14120° C. — — — — — — — — — — 150° C. — — — — — — — — — — Tensileelongation, % 550 470 250 200 450 500 500 480 450 530 Stress at 100%elongation, MPa — — — — — — — — — — Tearing strength, kN/m 60 52 30 3040 45 50 48 45 50 Compression set, % 52 65 75 90 70 65 60 65 60 70 Taberabrasion, mg 15 80 300 350 200 250 150 200 250 150 Oil resistance Weightchange, % — — — — — — — — — — Volume change, % — — — — — — — — — —Moldability ◯ ◯ X X Δ ◯ Δ ◯ Δ ◯ Bleedout property ◯ ◯ ◯ ◯ ◯ Δ ◯ Δ ◯ ΔAdhesive property, kg/25 mm vinyl chloride 5 1 — — — — — — — —polysulfone 4 1.5 — — — — — — — — polyphenylene ether 1 0 — — — — — — —— ABS 6 3 — — — — — — — — polystyrene 1 0 — — — — — — — — polymethylmethacrylate 3 1 — — — — — — — — polycarbonate 4 1.5 — — — — — — — —high-density polyethylene 0.5 0 — — — — — — — — polypropylene 0.5 0 — —— — — — — — nylon 5 1 — — — — — — — — *³Comparison Example in whichcomponent (n), TPAE, was kneaded all in step (I).

In Example 17, the elastomer composition was prepared according to thepresent process. The properties were good.

Meanwhile, in Comparison Example 45, component (n) was kneaded all instep (I) with the other components in the same composition as in Example17. The tensile strength, tensile elongation and tearing strengthdecreased and the taber abrasion increased considerably. The adhesiveproperty decreased for all of the resins. In Comparison Example 46,component (k), (l) and (m) were not blended. The tensile strength,tensile elongation and tearing strength decreased considerably and thetaber abrasion increased considerably. The moldability deterioratedconsiderably. In Comparison Example 47, organic peroxide (h) was notblended. The tensile strength, tensile elongation and tearing strengthdecreased considerably and the taber abrasion increased considerably.The moldability deteriorated considerably. In Comparison Example 48,component (k) was not blended, while in Comparison Example 49, theamount of component (k) was above the range of the present invention. Inboth compositions, the tensile strength and tearing strength decreasedconsiderably and the taber abrasion increased considerably. InComparison Example 48, the moldability deteriorated slightly, while inComparison Example 49, the bleedout property deteriorated slightly. InComparison Example 50, component (l) was not blended, while inComparison Example 51, the amount of component (l) was above the rangeof the present invention. In both compositions, the tensile strength andtearing strength decreased considerably and the taber abrasion increasedconsiderably. The bleedout property deteriorated slightly. In ComparisonExample 50, the moldability deteriorated slightly. In Comparison Example52, component (m) was not blended, while in Comparison Example 53, theamount of component (m) was above the range of the present invention. Inboth compositions, the tensile strength and tearing strength decreasedconsiderably and the taber abrasion increased considerably. InComparison Example 52, the moldability deteriorated slightly, while inComparison Example 53, the bleedout property deteriorated slightly.

Examples 18 to 20 and Comparison Examples 54 to 58

A polymethylpentene (TPX) was used as component (n).

Each component was used in the amount indicated in Table 17 in part byweight. In Examples 18 and 19, the whole amounts of components (a), (b),(c), (d), (k), (l), (m), (g) and (j) were introduced into a twin-screwextruder with an L/D of 62.5 together with the whole of component (n)and started to be melt kneaded at a kneading temperature of 180 to 220°C. and a screw rotation speed of 350 rpm. Next, the whole amounts ofcomponents (h) and (i) were side fed, melt kneaded and pelletized. InExample 20, the whole of components (a), (b), (c), (d), (k), (l), (m),(g) and (j) was introduced into a twin-screw extruder with an LID of62.5 and started to be melt kneaded at a kneading temperature of 180 to210° C. and a screw rotation speed of 350 rpm. Next, the whole ofcomponents (h) and (i) was side fed and the melt kneading was stillcontinued. Subsequently, the whole of component (n) was side fed, meltkneaded at 200 to 220° C. and pelletized. In both cases, the propertieswere then determined as in Example 11.

The results are as shown in Table 18.

TABLE 17 Amount of Component, Ex. Comparison Example part by weight 18*³19*³ 20*⁴ 54 55 56 57 58 (a) 100 100 100 100 100 100 100 100 (b) 100 100100 100 100 100 100 100 (c) 5 5 5 5 5 5 5 5 (d) 15 15 15 15 15 15 15 15(k) 10 10 10 0 40 10 10 10 (l) 4 4 4 0 4 20 4 4 (m) 4 4 4 0 4 0 20 4 (n)TPX 30 60 30 30 30 30 30 5 (g) 20 20 20 20 20 20 20 20 (h) 1.75 1.751.75 1.75 1.75 1.75 1.75 1.75 (i) 3.15 3.15 3.15 3.15 3.15 3.15 3.153.15 (j) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 *³Example in which component(n), TPX, was kneaded all in step (I). *⁴Example in which component (n),TPX, was kneaded all in step (II).

TABLE 18 Ex. Comparison Example Properties of the composition 18*³ 19*³20*⁴ 54 55 56 57 58 Specific gravity 0.92 0.91 0.92 0.92 0.92 0.92 0.920.92 Hardness, after HDA 15 seconds 68 80 68 70 76 66 66 45 Tensilestrength, MPa 23° C. 14.0 17.0 14.0 4.5 12.0 10.0 10.0 7.5 120° C. 1.21.6 1.2 0 0.5 0.3 0.3 0 150° C. 0.3 0.8 0.3 0 0 0 0 0 Tensileelongation, % 650 630 650 150 480 550 500 450 Stress at 100% elongation,MPa 4.8 5.2 4.8 3.8 4.0 4.2 4.0 2.3 Tearing strength, kN/m — — — — — — —— Compression set, % — — — — — — — — Taber abrasion, mg — — — — — — — —Oil resistance Weight change, % — — — — — — — — Volume change, % — — — —— — — — Moldability ◯ ◯ ◯ X ◯ ◯ ◯ ◯ Bleedout property ◯ ◯ ◯ ◯ Δ Δ Δ ◯*³Example in which component (n), TPX, was kneaded all in step (I).*⁴Example in which component (n), TPX, was kneaded all in step (II).

In Examples 18 to 20, the elastomer compositions were prepared accordingto the present process. In Example 18 and 19, component (n) was kneadedall in step (I) and the amount of (n) was varied within the range of thepresent invention. When the amount of (n) blended was increased, thehardness, tesile strength and elongastion stress increased. In Example20, component (n) was kneaded all in step (II). It was found that in thecase where polymethylpentene (TPX) was used as component (n), there wasno change in properties of the elastomers obtained, whether the whole ofcomponent (n) was melt kneaded in step (I) or in step (II).

Meanwhile, in Comparison Example 54, component (k) was not blended,while in Comparison Example 55, the amount of component (k) was abovethe range of the present invention. In both compositions, the hardnessincreased and the tensile strength, tensile elongation and elongationstress decreased considerably. In Comparison Example 54, the moldabilitydeteriorated considerably while in Comparison Example 55, the bleedoutproperty deteriorated slightly. In Comparison Example 56, the amount ofcomponent (l) was above the range of the present invention and component(m) was not blended. The tensile strength, tensile elongation andelongation stress decreased considerably and the bleedout propertydeteriorated slightly. In Comparison Example 57, the amount of component(m) was above the range of the present invention. The tensile strength,tensile elongation and elongation stress decreased and the bleedoutproperty deteriorated slightly. In Comparison Example 58, the amount ofcomponent (n) was below the range of the present invention. Thehardness, tensile strength, tensile elongation and elongation stressdecreased considerably.

Examples 21 to 23 and Comparison Examples 59 to 66

Nylon-6 was used as component (n).

Each component was used in the amount indicated in Table 19 in part byweight. In Examples 21 and 22, the whole of component (n) was meltkneaded in step (I), while in Example 23, the whole of component (n) wasmelt kneaded in step (11). The melt kneading and the determination ofthe properties were carried out in the same conditions as in the case ofpolymethylpentene mentioned above.

The results are as shown in Table 20.

TABLE 19 Amount of Component, Ex. Comparison Example part by weight 21*³22*³ 23*⁴ 59 60 61 62 63 64 65 66 (a) 100 100 100 100 100 100 100 100100 100 100 (b) 100 100 100 100 100 100 100 100 100 100 100 (c) 5 5 5 55 5 5 5 5 5 5 (d) 15 15 15 15 15 15 15 15 15 15 15 (k) 10 10 10 0 40 1010 10 10 10 10 (l) 4 4 4 4 4 0 20 4 4 4 4 (m) 4 4 4 4 4 4 4 0 20 4 4 (n)nylon-6 30 60 30 30 30 30 30 30 30 30 5 (g) 20 20 20 20 20 20 20 20 2020 20 (h) 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 1.75 0 1.75 (i) 3.153.15 3.15 3.15 3.15 3.15 3.15 3.15 3.15 0 3.15 (j) 0.4 0.4 0.4 0.4 0.40.4 0.4 0.4 0.4 0.4 0.4 *³Example in which component (n), nylon-6, waskneaded all in step (I). *⁴Example in which component (n), nylon-6, waskneaded all in step (II)

TABLE 20 Ex. Comparison Example Properties of the composition 21*³ 22*³23*⁴ 59 60 61 62 63 64 65 66 Specific gravity 0.93 0.93 0.93 0.93 0.930.93 0.93 0.93 0.93 0.93 0.92 Hardness, after HDA 15 seconds 70 82 70 7066 70 66 70 68 55 48 Tensile strength, MPa 23° C. 10.0 15.0 10.0 7.0 9.08.0 7.0 9.0 8.5 3.0 5.0 120° C. 1.5 1.9 1.5 0.7 0.8 0.8 0.8 0.8 0.9 0 0150° C. 0.5 0.8 0.5 0 0 0 0 0 0 0 0 Tensile elongation, % 450 500 450400 420 380 350 400 420 250 350 Stress at 100% elongation, MPa 4.5 4.84.5 3.5 3.3 3.5 3.0 3.8 3.5 1.3 1.8 Tearing strength, kN/m — — — — — — —— — — — Compression set, % 60 63 60 70 65 65 70 65 70 80 70 Taberabrasion, mg 100 60 100 200 250 200 200 200 250 450 400 Oil resistanceWeight change, % 30 25 30 50 — — — — — 100 80 Volume change, % 25 18 2542 — — — — — 90 70 Moldability ◯ ◯ ◯ X ◯ ◯ ◯ ◯ ◯ Δ ◯ Bleedout property ◯◯ ◯ ◯ Δ Δ Δ ◯ ◯ ◯ ◯ *³Example in which component (n), nylon-6, waskneaded all in step (I). *⁴Example in which component (n), nylon-6, waskneaded all in step (II)

In Examples 21 to 23, the elastomer compositions were prepared accordingto the present process. In Examples 21 to 22, component (n) was kneadedall in step (I) and the amount of (n) was varied within the range of thepresent invention. When the amount of (n) blended was increased, thehardness, tesile strength, tensile elongation, elongastion stress andcompression set increased, and the oil resistance improved, and thetaber abrasion decreased. In Example 23, component (n) was kneaded allin step (II). It was found that in the case where nylon-6 was used ascomponent (n), there was no change in properties of the elastomersobtained, whether the whole of component (n) was melt kneaded in step(I) or in step (II).

Meanwhile, in Comparison Example 59, component (k) was not blended,while in Comparison Example 60, the amount of component (k) was abovethe range of the present invention. In Comparison Example 59, thetensile strength, tensile elongation and elongation stress decreased andthe taber abrasion increased considerably. The oil resistancedeteriorated considerably. The moldability deteriorated alsoconsiderably. In Comparison Example 60, the hardness, tensile strength,tensile elongation and elongation stress decreased and the taberabrasion increased considerably. The bleedout property deterioratedslightly. In Comparison Example 61, component (l) was not blended, whilein Comparison Example 62, the amount of component (l) was above therange of the present invention. In Comparison Example 61, the tensilestrength, tensile elongation and elongation stress decreased and thetaber abrasion increased considerably. The bleedout propertydeteriorated slightly. In Comparison Example 62, the hardness, tensilestrength, tensile elongation and elongation stress decreased and thetaber abrasion increased considerably. The bleedout propertydeteriorated slightly. In Comparison Example 63, component (m) was notblended, while in Comparison Example 64, the amount of component (m) wasabove the range of the present invention. In both compositions, thetensile strength, tensile elongation and elongation stress decreased andthe taber abrasion increased considerably. In Comparison Example 65,component (h), organic peroxide, was not blended. The hardness, tensilestrength, tensile elongation and elongation stress decreasedconsiderably and the oil resistance deteriorated considerably. The taberabrasion increased considerably. The moldability deteriorated also. InComparison Example 66, the amount of component (n) was below the rangeof the present invention. The hardness, tensile strength, tensileelongation and elongation stress decreased considerably. The oilresistance deteriorated considerably and the taber abrasion increasedconsiderably.

What is claimed is:
 1. A process for the preparation of a thermoplasticelastomeric resin composition comprising melt kneading (a) 100 parts byweight of block copolymer consisting of at least two polymeric blocks(A) composed mainly of a vinyl aromatic compound and at least onepolymeric block (B) composed mainly of at least one of a conjugateddiene compound and a hydrogenated block copolymer obtained byhydrogenating said block copolymer, (b) 20 to 240 parts by weight of anon-aromatic softening agent for rubber in which from 0 to 30% of thewhole carbon atoms are in aromatic rings, (d) 5 to 100 parts by weightof a peroxide decomposing olefinic resin selected from the groupconsisting of polypropylenes and copolymers of propylene with a smalleramount of another α-olefin, characterized in that the process comprisesthe following steps: (I) melt kneading the whole amounts of components(a) and (b) and the whole amounts of (k) 1 to 30 parts by weight ofliquid polybutadiene, (l) 0.01 to 15 parts by weight of an unsaturatedglycidyl compound or derivative thereof, and (m) 0.01 to 15 parts byweight of an unsaturated carboxylic acid or derivative thereof and apart of component (d), and, at the same time or subsequently, meltkneading these with the whole of (h) 0.1 to 3.5 parts by weight of anorganic peroxide per 100 parts by weight of a total amount of components(a), (b), (d) and (k), and (II) melt kneading the product obtained fromstep (I) with the remaining part of component (d).
 2. The process asdescribed in claim 1, wherein a weight ratio of the amount of component(d) blended in step (I) and that in step (II) is 10:90 to 90:10.
 3. Theprocess as described in claim 1, wherein the whole of (c) at most 100parts by weight of a peroxide-crosslinking olefinic resin selected fromthe group consisting of high density polyethylene, low densitypolyethylene, linear low density polyethylene, ultra-low densitypolyethylene, ethylene-propylene copolymer, ethylene-vinyl acetatecopolymer, ethylene-acrylate copolymer, ethylene-propylene copolymericrubber and ethylene-propylene-non-conjugated diene copolymeric rubber isalso melt kneaded first in step (I), where the amount of the organicperoxide (h) is 0.1 to 3.5 parts by weight per 100 parts by weight of atotal amount of components (a), (b), (c), (d) and (k).
 4. A process forthe preparation of a thermoplastic elastomeric resin compositioncomprising melt kneading (a) 100 parts by weight of a block copolymerconsisting of at least two polymeric blocks (A) composed mainly of avinyl aromatic compound and at least one polymeric block (B) composedmainly of a conjugated diene compound, and/or a hydrogenated blockcopolymer obtained by hydrogenating said block copolymer, (b) 20 to 240parts by weight of a non-aromatic softening agent for rubber in whichfrom 0 to 30% of the whole carbon atoms are in aromatic rings, (d) 5 to100 parts by weight of peroxide-decomposing olefinic resin selected fromthe group consisting of polypropylenes and copolymers of propylene witha smaller amount of another β-olefin, characterized in that the processcomprises the following steps: (I) melt kneading the whole amounts ofcomponents (a), (b) and (d) and the whole amounts of (k) 1 to 30 partsby weight of liquid polybutadiene, (l) 0.01 to 15 parts by weight of anunsaturated glycidyl compound or derivative thereof, and (m) 0.01 to 15parts by weight of an unsaturated carboxylic acid or derivative thereof,or the whole amounts of components (a), (b), (d), (k), (l) and (m) andthe whole or a part of (n) 10 to 1,500 parts by weight of at least onematerial selected from the group consisting of polyester (co)polymers,polyurethane (co)polymers, polyamide (co)polymers and polymethylpentene(co)polymers, and, at the same time or subsequently, melt kneading thesewith the whole of (h) 0.1 to 3.5 parts by weight of an organic peroxideper 100 parts by weight of a total amount of components of (a), (b), (d)and (k), and (II) further melt kneading the product obtained from step(I) with the remaining part of component (n), if any.
 5. The process asdescribed in claim 4, wherein component (n) is polymethylpentene ornylon-6, and the whole or a part of component (n) is melt kneaded instep (I) or the whole of component (n) is melt kneaded in step (II)without melt kneading component (n) in step (I).
 6. The process asdescribed in claim 4, wherein a part or none of component (n) is meltkneaded in step (I) and the remaining part of component (n) is meltkneaded in step (II).
 7. The process as described in claim 4, wherein apart or none of component (n) is melt kneaded in step (I) and theremaining part of component (n) is melt kneaded in step (II), wherein aweight ratio of component (n) blended in step (I) and that in step (II)is 10:90 to 0:100.
 8. The process as described in claim 4, wherein apart or none of component (n) is melt kneaded in step (l) and theremaining part of component (n) is melt kneaded in step (II), whereincomponent (n) is a thermoplastic polyester elastomer, thermoplasticpolyamide elastomer or thermoplastic polyurethane elastomer.
 9. Theprocess as described in claim 4, wherein (i) 0.1 to 3.5 parts by weightof a crosslinking aid per 100 parts by weight of a total amount ofcomponents (a), (b), (d) and (k) are kneaded together with component (h)in step (I).
 10. The process as described in claim 4, wherein the wholeof (c) at most 100 parts by weight of a peroxide-crosslinking olefinicresin selected from the group consisting of high density polyethylene,low density polyethylene, linear low density polyethylene, ultra-lowdensity polyethylene, ethylene-propylene copolymer, ethylene-vinylacetate copolymer, ethylene-acrylate copolymer, ethylene-propylenecopolymeric rubber and ethylene-propylene-non-conjugated dienecopolymeric rubber are also melt kneaded first in step (I), where theamount of the organic peroxide (h) is 0.1 to 3.5 parts by weight per 100parts by weight of a total amount of components (a), (b), (c), (d) and(k).
 11. A thermoplastic elastomeric resin composition comprising (a)100 parts by weight of a block copolymer consisting of at least twopolymeric blocks (A) composed mainly of a vinyl aromatic compound and atleast one polymeric block (B) composed mainly of a conjugated dienecompound, and/or a hydrogenated block copolymer obtained byhydrogenating said block copolymer, (b) 20 to 240 parts by weight of anon-aromatic softening agent for rubber in which from 0 to 30% of thewhole carbon atoms are in aromatic rings, and (d) 5 to 100 parts byweight of a peroxide-decomposing olefinic resin selected form the groupconsisting of polypropylenes and copolymers of polypropylene with asmall amount of another β-olefin characterized in that said compositionfurther comprises (k) 1 to 30 parts by weight of liquid polybutadiene,(l) 0.01 to 15 parts by weight of an unsaturated glycidyl compound orderivative thereof, and (m) 0.01 to 15 parts by weight of an unsaturatedcarboxylic acid or derivative thereof.
 12. The thermoplastic elastomericresin composition as described in claim 11, wherein the compositionfurther comprises (n) 10 to 1,500 parts by weight of at least onematerial selected from the group consisting of polyester (co)polymers,polyurethane (co)polymers, polyamide (co)polymers and polymethylpentene(co)polymers.
 13. The thermoplastic elastomeric resin composition asdescribed in claim 11, wherein the composition further comprises (c) atmost 100 parts by weight of a peroxide-crosslinking type olefinic resinselected from the group consisting of high density polyethylene, lowdensity polyethylene, linear low density poolyethylene, ultra-lowdensity polyethylene, ethylene-propylene copolymer, ethylene-vinylacetate copolymer, ethylene-acrylate copolymer, ethylene-propylenecopolymeric rubber and ethylene-propylene-non-conjugated dienecopoylmeric rubber.